CN113964383A - Lithium ion battery positive electrode material additive, preparation method and application thereof - Google Patents
Lithium ion battery positive electrode material additive, preparation method and application thereof Download PDFInfo
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- CN113964383A CN113964383A CN202111074531.1A CN202111074531A CN113964383A CN 113964383 A CN113964383 A CN 113964383A CN 202111074531 A CN202111074531 A CN 202111074531A CN 113964383 A CN113964383 A CN 113964383A
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- lithium ion
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- ion battery
- lithium
- positive electrode
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- 239000000654 additive Substances 0.000 title claims abstract description 91
- 230000000996 additive effect Effects 0.000 title claims abstract description 91
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 title claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001868 water Inorganic materials 0.000 claims abstract description 28
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 24
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 24
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 24
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 24
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 239000002109 single walled nanotube Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 31
- 239000011572 manganese Substances 0.000 claims description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 26
- 239000011230 binding agent Substances 0.000 claims description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 21
- 229910052748 manganese Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 10
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 229910008026 Li1+x+yAlxTi2-xSiyP3-yO12 Inorganic materials 0.000 claims description 4
- 229910008043 Li1+x+yAlxTi2−xSiyP3-yO12 Inorganic materials 0.000 claims description 4
- 229910006188 Li1+x+yAlxTi2−xSiyP3−yO12 Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 17
- 238000012360 testing method Methods 0.000 description 64
- 125000004122 cyclic group Chemical group 0.000 description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 27
- 239000006256 anode slurry Substances 0.000 description 25
- 239000011267 electrode slurry Substances 0.000 description 22
- 230000014759 maintenance of location Effects 0.000 description 20
- 239000002033 PVDF binder Substances 0.000 description 16
- 230000001351 cycling effect Effects 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 238000011056 performance test Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229920002125 Sokalan® Polymers 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000007600 charging Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- -1 nanosilica Chemical compound 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery anode material additive, a preparation method and application thereof, wherein the preparation method comprises the following steps: A) heating and mixing isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide, ammonium dihydrogen phosphate and water to obtain a mixed solution; B) adjusting the pH value of the mixed solution to 9.6-10.0, and filtering and drying the obtained precipitation mixed solution; C) and grinding the dried precipitate, and burning under the condition of protective gas to obtain the lithium ion battery cathode material additive with the general formula shown in the formula (1). The lithium ion battery cathode material additive prepared by the invention can effectively improve the rate capability of the battery, increase the gram capacity exertion of the cathode material and realize the stable circulation of the battery under high rate. Meanwhile, the preparation method provided by the invention is simple and easy to operate and is easy to introduce into the existing battery system.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery anode material additive, and a preparation method and application thereof.
Background
At present, the method for improving the rate performance of the ion battery is generally to add a composite conductive agent or carry out coating treatment on the material layer. For adding the composite conductive agent, the effect is not obviously improved, 0.5C circulation can hardly be carried out, and the high energy density is required by the current lithium ion battery, so that the content of active substances cannot be greatly reduced; meanwhile, the novel composite conductive agent has high cost, and the moisture of the pole piece is difficult to remove in the process of adding the single-wall carbon tube, so that the serious gas generation problem can be caused in the later stage especially in a lithium-rich battery system. Chinese patent CN108448089A discloses a scheme for coating a material layer, in which a lithium-rich material with a nano size is obtained by high-energy ball milling, and the specific surface area is increased, thereby improving the rate capability. However, the particles obtained by the method are difficult to homogenize in the process of scale-up production, lithium battery slurry is difficult to obtain, and the particles are extremely easy to crush in the rolling process and are separated from the reality; meanwhile, the capacity of 0.1 gram of C is 265mAh/g, the capacity of 0.2 gram of C is 250mAh/g, the capacity of 0.5 gram of C is 230mAh/g, the capacity of 1 gram of C is 200mAh/g, the capacity of 2 gram of C is 175mAh/g, the capacity of 4 gram of C is 140mAh/g, and the gram capacity is still to be improved.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide an additive for a positive electrode material of a lithium ion battery, a preparation method and an application thereof, and the lithium ion battery prepared from the positive electrode sheet added with the additive has excellent electrochemical performance.
The invention provides a preparation method of a lithium ion battery anode material additive, which comprises the following steps:
A) heating and mixing isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide, ammonium dihydrogen phosphate and water to obtain a mixed solution;
B) adjusting the pH value of the mixed solution to 9.6-10.0, and filtering and drying the obtained precipitation mixed solution;
C) grinding the dried precipitate, and burning under the condition of protective gas to obtain the lithium ion battery anode material additive with the general formula shown in the formula (1);
Li1+x+yAlxTi2-xSiyP3-yO12 (1)；
wherein 0< x <2, 0< y < 3.
Preferably, the molar ratio of isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide and ammonium dihydrogen phosphate is 0.5-1.5: 2.5-3.5: 0.5-1.5: 0.5-1.5: 4.5 to 5.5.
Preferably, in step a), the heating and mixing of isopropyl titanate, lithium oxalate, aluminum nitrate, ammonium dihydrogen phosphate and water comprises:
firstly, stirring and mixing isopropyl titanate, aluminum nitrate and part of water, then adding lithium oxalate, nano silicon dioxide, ammonium dihydrogen phosphate and the rest water, and stirring and mixing under the condition of heating;
the heating temperature is 75-85 ℃.
Preferably, the dosage ratio of the total mass of the isopropyl titanate and the aluminum nitrate to part of water is 0.5-2 g: 90-110 mL;
the dosage ratio of the total mass of the lithium oxalate, the nano silicon dioxide and the ammonium dihydrogen phosphate to the rest water is 0.5-1.8 g: 40-60 mL.
Preferably, in the step B), the reagent for adjusting the pH value of the mixed solution is ammonia water;
the drying temperature is 115-125 ℃, and the drying time is 22-26 h.
Preferably, in the step C), the burning temperature is 880-920 ℃, and the time is 14-18 h;
after the firing, the method further comprises the following steps: naturally cooling to room temperature, and grinding again;
the grinding frequency of the secondary grinding is 480-520 Hz, and the time is 10-14 h.
The invention also provides the lithium ion battery positive electrode material additive prepared by the preparation method.
The invention also provides a lithium ion battery positive plate which is prepared by uniformly mixing the raw materials comprising the positive electrode material, the additive, the conductive carbon black, the single-walled carbon nanotube and the binder and coating the mixture on a current collector;
the positive electrode material comprises a lithium-rich manganese-based layered material, single crystal lithium nickel manganese oxide, lithium iron phosphate or a high-voltage ternary material;
the additive is the additive of the lithium ion battery positive electrode material.
Preferably, the mass ratio of the positive electrode material to the additive is 92-98: 0.1 to 5;
the mass ratio of the positive electrode material to the conductive carbon black to the single-walled carbon nanotube to the binder is 92-98: 0.8-1.5: 0.1-0.2: 1.5.
the invention also provides a lithium ion battery which is characterized by comprising an anode, a cathode, a diaphragm and electrolyte, wherein the anode is the lithium ion battery anode plate.
The invention provides a preparation method of a lithium ion battery anode material additive, which comprises the following steps of A) heating and mixing isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide, ammonium dihydrogen phosphate and water to obtain a mixed solution; B) adjusting the pH value of the mixed solution to 9.6-10.0, and filtering and drying the obtained precipitation mixed solution; C) and grinding the dried precipitate, and burning under the condition of protective gas to obtain the lithium ion battery cathode material additive with the general formula shown in the formula (1). The lithium ion battery cathode material additive prepared by the invention can effectively improve the rate capability of the battery, increase the gram capacity exertion of the cathode material and realize the stable circulation of the battery under high rate. Meanwhile, the preparation method provided by the invention is simple and easy to operate and is easy to introduce into the existing battery system.
Drawings
Fig. 1 shows the first efficiency and medium voltage after the soft package battery of example 2 of the present invention is formed into a capacity;
fig. 2 is a rate performance curve for button cells of example 2 of the present invention and comparative example 1;
fig. 3 is a cycle curve of a full cell of example 2 of the present invention at 0.5C rate;
fig. 4 is a capacity retention rate of the full cell of example 2 of the present invention cycled 325 times at 0.5C rate;
fig. 5 is a 2000-fold SEM image of the positive electrode sheet of example 5 of the present invention;
fig. 6 is a 1000-fold SEM image of the positive electrode sheet of example 5 of the present invention;
fig. 7 is a 10000-fold SEM image of the positive electrode sheet of example 6 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a lithium ion battery anode material additive, which comprises the following steps:
A) heating and mixing isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide, ammonium dihydrogen phosphate and water to obtain a mixed solution;
B) adjusting the pH value of the mixed solution to 9.6-10.0, and filtering and drying the obtained precipitation mixed solution;
C) grinding the dried precipitate, and burning under the condition of protective gas to obtain the lithium ion battery anode material additive with the general formula shown in the formula (1);
Li1+x+yAlxTi2-xSiyP3-yO12 (1)；
wherein 0< x <2, 0< y < 3.
The method comprises the steps of heating and mixing isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide, ammonium dihydrogen phosphate and water to obtain a mixed solution.
In some embodiments of the invention, the molar ratio of isopropyl titanate, lithium oxalate, aluminum nitrate, nano-silica and ammonium dihydrogen phosphate is 0.5-1.5: 2.5-3.5: 0.5-1.5: 0.5-1.5: 4.5 to 5.5. In certain embodiments, the molar ratio of isopropyl titanate, lithium oxalate, aluminum nitrate, nanosilica, and ammonium dihydrogen phosphate is 1: 3: 1: 1: 5.
in certain embodiments of the present invention, the water is deionized water.
In certain embodiments of the present invention, heating and mixing isopropyl titanate, lithium oxalate, aluminum nitrate, nanosilica, ammonium dihydrogen phosphate, and water comprises:
firstly, stirring and mixing isopropyl titanate, aluminum nitrate and part of water, then adding lithium oxalate, nano silicon dioxide, ammonium dihydrogen phosphate and the rest of water, and stirring and mixing under the condition of heating.
The stirring speed of the stirring and mixing is not particularly limited in the present invention, and may be any stirring speed known to those skilled in the art.
In some embodiments of the present invention, the heating temperature is 75-85 ℃. In certain embodiments, the temperature of the heating is 80 ℃.
In some embodiments of the invention, the isopropyl titanate, the aluminum nitrate and the part of water are stirred and mixed for 0.5-1 h. In some embodiments of the invention, the time for adding lithium oxalate, nano-silica, ammonium dihydrogen phosphate and the rest of water and stirring and mixing under the heating condition is 0.5-1 h.
In some embodiments of the invention, the ratio of the total mass of the isopropyl titanate and the aluminum nitrate to the part of water is 0.5-2 g: 90-110 mL. In certain embodiments, the ratio of the total mass of isopropyl titanate and aluminum nitrate to the amount of part of water is 1 g: 100 mL.
In some embodiments of the invention, the ratio of the total mass of the lithium oxalate, the nano-silica and the ammonium dihydrogen phosphate to the amount of the residual water is 0.5-1.8 g: 40-60 mL. In certain embodiments, the ratio of the total mass of lithium oxalate, nanosilica and ammonium dihydrogen phosphate to the amount of remaining water is 1 g: 50 mL.
And after obtaining a mixed solution, adjusting the pH value of the mixed solution to 9.6-10.0, and filtering and drying the obtained precipitation mixed feed liquid.
In some embodiments of the present invention, the agent for adjusting the pH of the mixed solution is ammonia.
In the invention, the pH value of the mixed solution is adjusted to 9.6-10.0, and precipitates can be formed. In certain embodiments of the invention, the pH of the mixed liquor is adjusted to 9.6.
The method of filtration is not particularly limited in the present invention, and a filtration method known to those skilled in the art may be used.
In certain embodiments of the invention, the filtration further comprises washing. The washing method of the present invention is not particularly limited, and a washing method known to those skilled in the art may be used.
In some embodiments of the present invention, the drying temperature is 115-125 ℃ and the drying time is 22-26 hours. In certain embodiments of the invention, the drying is performed in a forced air drying oven.
After drying, grinding the dried precipitate, and burning under the condition of protective gas to obtain the lithium ion battery anode material additive with the general formula shown in the formula (1);
Li1+x+yAlxTi2-xSiyP3-yO12 (1)；
wherein 0< x <2, 0< y < 3.
In certain embodiments of the invention, the method of milling is ball milling. In some embodiments of the invention, the rotation speed of the ball mill is 680-720 r/min, and the time is 2.5-3.5 h. In certain embodiments, the rotational speed of the ball mill is 700 r/min. In certain embodiments, the ball milling time is 3 hours.
In certain embodiments, the ball milling is performed in a zirconia ball mill pot. In certain embodiments of the present invention, the particle size of the milled precipitate is 80 to 150 nm.
In certain embodiments of the invention, the shielding gas is argon.
In some embodiments of the invention, the burning temperature is 880-920 ℃ and the time is 14-18 h. In certain embodiments, the firing is performed in a tube furnace. In certain embodiments, the temperature of the burn is 900 ℃. In certain embodiments, the time to burn is 16 hours.
In some embodiments of the present invention, before burning under the condition of the shielding gas, the method further comprises: heating to the burning temperature under the condition of protective gas.
In some embodiments of the present invention, the heating rate is 2-4 ℃/min. In certain embodiments, the rate of heating is 3 ℃/min.
In some embodiments of the present invention, after the burning, the method further comprises: naturally cooling to room temperature, and grinding again.
In some embodiments of the present invention, the frequency of the regrinding is 480 to 520Hz, and the time is 10 to 14 hours. In certain embodiments, the regrinding is performed in a sand mill. In certain embodiments, the regrinding frequency is 500 Hz. In certain embodiments, the regrinding time is 12 hours.
In certain embodiments of the present invention, in formula (1), x is 0.5 or 1 and y is 0.5, 1 or 2. Preferably, in formula (1), x is 1 and y is 1.
In certain embodiments of the present invention, the lithium ion battery positive electrode material additive having the general formula shown in formula (1) is a solid powder.
The invention also provides the lithium ion battery positive electrode material additive prepared by the preparation method.
The invention also provides a lithium ion battery positive plate which is prepared by uniformly mixing the raw materials comprising the positive electrode material, the additive, the conductive carbon black, the single-walled carbon nanotube and the binder and coating the mixture on a current collector;
the positive electrode material comprises a lithium-rich manganese-based layered material, single crystal lithium nickel manganese oxide, lithium iron phosphate or a high-voltage ternary material;
the additive is the additive of the lithium ion battery positive electrode material.
In certain embodiments of the invention, the lithium-rich manganese-based layered material is Li1.44Mn0.544Ni0.136Co0.136O2、Li1.38Mn0.656Ni0.172Co0.171O2Or Li1.348Mn0.66Ni0.17Co0.167O2. In the present invention, the lithium-rich manganese-based layered material may be commercially available, and in some embodiments of the present invention, the lithium-rich manganese-based layered material is obtained from Ningbo materials institute of science and technology and engineering, China.
In some embodiments of the invention, the single-crystal lithium nickel manganese oxide is single-crystal 532 lithium nickel manganese oxide.
In certain embodiments of the invention, the binder is PVDF.
In certain embodiments of the present invention, the mass ratio of the positive electrode material to the additive is 92-98: 0.1 to 5. In certain embodiments, the mass ratio of the positive electrode material to the additive is 97.5: 0.1, 97.1: 0.5, 96.6: 1. 95.1: 2.5 or 92.6: 5.
in some embodiments of the invention, the mass ratio of the positive electrode material, the conductive carbon black, the single-walled carbon nanotubes and the binder is 92-98: 0.8-1.5: 0.1-0.2: 1.5. in certain embodiments, the mass ratio of the cathode material, conductive carbon black, single-walled carbon nanotubes, and binder is 97.5: 0.8: 0.1: 1.5, 97.1: 0.8: 0.1: 1.5, 96.6: 0.8: 0.1: 1.5, 95.1: 0.8: 0.1: 1.5 or 92.6: 0.8: 0.1: 1.5.
in certain embodiments of the invention, the current collector is aluminum foil. In certain embodiments, the aluminum foil is 12 μm thick.
In some embodiments of the invention, the lithium ion battery positive plate is prepared according to the following method:
a) uniformly mixing a positive electrode material, an additive, conductive carbon black, a single-walled carbon nanotube and a binder to obtain positive electrode slurry;
b) and coating the positive electrode slurry on a current collector, and tabletting to obtain the lithium ion battery positive plate.
In certain embodiments of the invention, the positive electrode slurry has a slurry viscosity of 4500mPa S, with a solids content of 63%.
The raw materials and the proportion adopted in the preparation method of the lithium ion battery positive plate are the same as above, and are not described again here.
In certain embodiments of the present invention, the thickness of the coating is 240 μm.
In some embodiments of the invention, the thickness of the positive plate of the lithium ion battery is 200 μm.
The invention also provides a lithium ion battery which is characterized by comprising an anode, a cathode, a diaphragm and electrolyte, wherein the anode is the lithium ion battery anode plate.
In some embodiments of the present invention, a negative electrode sheet for a negative electrode is prepared according to the following method:
and coating the negative electrode slurry on copper foil, and tabletting to obtain the lithium ion battery negative electrode sheet.
In certain embodiments of the present invention, the negative electrode slurry comprises silica, graphite, conductive carbon black, single-walled carbon nanotubes, and polyacrylic acid; the mass ratio of the silica to the conductive carbon black to the single-walled carbon nanotube to the polyacrylic acid is 51: 44.8: 1.04: 0.06: 3.1. in certain embodiments of the invention, the gram capacity of the silica and graphite in the anode slurry is 1000 mAh/g.
In certain embodiments of the present invention, the copper foil has a thickness of 6 μm.
In certain embodiments of the present invention, the thickness of the coating is 125 μm.
In some embodiments of the present invention, the thickness of the lithium ion battery negative electrode sheet is 110 μm.
In certain embodiments of the invention, the membrane is an asahi chemical compound membrane celgard 2000.
In certain embodiments of the present invention, the electrolyte is china tavero electrolyte 4750 FB.
In certain embodiments of the invention, the positive electrode, negative electrode, separator, and electrolyte are assembled into a pouch cell or button cell.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
The additive for the positive electrode material with the general formula shown in the formula (1) is applied to a liquid battery system, and mainly utilizes the characteristic of a fast ion conductor of the additive to improve some positive electrode materials with lower intrinsic ionic conductivity, and utilizes the ion conduction characteristic of the additive and the cross-linking and complexing of the additive and active substances in electrode materials and conductive additives to improve ion transmission, so that the rate capability is greatly improved.
In order to further illustrate the present invention, the following will describe in detail the lithium ion battery positive electrode material additive, its preparation method and application provided by the present invention with reference to the examples, but it should not be construed as limiting the scope of the present invention.
Example 1
The molar ratio of isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide and ammonium dihydrogen phosphate is 1: 3: 1: 1: 5;
1) adding isopropyl titanate, aluminum nitrate and part of deionized water into a reaction container, and stirring for 0.8 h; the dosage ratio of the total mass of the isopropyl titanate and the aluminum nitrate to part of water is 1 g: 100 mL;
2) then adding lithium oxalate, nano silicon dioxide, ammonium dihydrogen phosphate and the rest deionized water, stirring, heating to 80 ℃, and stirring for 0.5h to obtain a mixed solution; the dosage ratio of the total mass of the lithium oxalate, the nano silicon dioxide and the ammonium dihydrogen phosphate to the rest water is 1 g: 50 mL;
3) adding ammonia water into the mixed solution to adjust the pH value to 9.6, forming a precipitate, filtering and washing;
4) drying in a forced air drying oven at 120 ℃ for 24 h;
5) ball-milling for 3h in a zirconia ball-milling tank at 700r/min, screening to obtain powder with the particle size of 80-150 nm, heating to 900 ℃ at the speed of 3 ℃/min in a tubular furnace under the condition of argon, burning for 16h, and naturally cooling to room temperature;
6) and then grinding the mixture for 12 hours in a sand mill at the frequency of 500Hz to obtain solid powder, namely the lithium ion battery cathode material additive, which has the general formula shown in the formula (1), wherein x is 1, and y is 1.
Example 2
Mixing a lithium-rich manganese-based layered material LRM, an additive (the additive of the lithium ion battery cathode material prepared in example 1), conductive carbon black SP, single-walled carbon nanotubes SWCNT and a binder PVDF according to a mass ratio of 97.5: 0.1: 0.8: 0.1: 1.5, uniformly mixing to obtain positive electrode slurry; the lithium-rich manganese-based layered material LRM is Li1.44Mn0.544Ni0.136Co0.136O2(ii) a The slurry viscosity of the positive electrode slurry was 4500mPa · S, and the solid content was 63%;
coating the positive electrode slurry on an aluminum foil with the thickness of 12 microns, coating the aluminum foil with the thickness of 240 microns, and tabletting to obtain a positive plate with the thickness of 200 microns;
silica SiO, graphite, conductive carbon black SP, single-walled carbon nanotube SWCNT and polyacrylic acid PAA are mixed according to the mass ratio of 51: 44.8: 1.04: 0.06: 3.1, uniformly mixing to obtain negative electrode slurry; in the negative electrode slurry, the gram capacity of the silicon monoxide and the graphite is 1000 mAh/g;
coating the negative electrode slurry on a copper foil with the thickness of 6 microns, coating the copper foil with the thickness of 125 microns, and tabletting to obtain a negative electrode plate with the thickness of 110 microns;
and respectively assembling the negative plate, the positive plate, the Xuhuarong diaphragm celgard2000 and electrolyte (Chinese Thailand Huarong 4750FB) into a soft-package battery and a button battery, and standing the soft-package battery for 24 hours at a high temperature of 45 ℃.
After standing at a high temperature, the first charge-discharge efficiency and the medium voltage were recorded by a chemical composition-volume operation, and the results are shown in fig. 1. Fig. 1 shows the first charge-discharge efficiency and the medium voltage after the soft-package battery of example 2 of the present invention is formed into a partial volume. In fig. 1, the discharge curves of 0.5C, 1C and 0.2C almost coincide (fig. 1 includes the discharge curve and the charge curve, the magnification of the discharge curve from top to bottom is 0.2C, 0.5C, 1C, the blue line is 0.2C, the red line is 0.5C, the green line is 1C, the uppermost charge curve corresponds to the magnification of 0.2C, that is, the blue line is 0.2C, and the charge curves of 0.5C and 1C coincide, that is, the charge curves of 0.5C and 1C are black lines), and the capacity occupancy reaches 100%.
The method comprises the following specific steps: standing the battery after standing at high temperature for t1, then charging to U1 with a current constant current of 0.02C, then discharging to U2 with a current constant current of 0.1C, then charging to a current of 0.02C with a voltage constant voltage of U2, standing for t2, discharging to U3 with a voltage constant current of 0.1C, decompressing, exhausting and sealing, and completing the capacity of chemical components; t1 is 12h, U1 is 3.5V, U2 is 4.6V, U3 is 2.5V, and t2 is 3 min.
The button cell prepared in example 2 was subjected to a rate test with a LAND electrochemical tester under room temperature and a constant current charging and discharging voltage of 2-4.6V, and the test results are shown in FIG. 2. Fig. 2 is a rate performance curve for button cells of example 2 of the invention and comparative example 1. Here, additive PW01 represents the rate performance curve of the button cell of example 2, and control represents the rate performance curve of the button cell of comparative example 1. As can be seen from FIG. 2, the PW01 additive was added to give a 0.1C g capacity of 300mAh/g, a 0.2C g capacity of 275mAh/g, a 1C g capacity of 240mAh/g, and a 2C g capacity of 220 mAh/g.
In this embodiment, a LAND electrochemical tester is used to test the electrochemical performance of the full cell, the test condition is room temperature, the constant current charging and discharging voltage is 2-4.6V, the cycle performance of the full cell is tested, the obtained cycle curve is shown in FIG. 3, and the obtained capacity retention rate is shown in FIG. 4.
Fig. 3 is a cycle curve of a full cell of example 2 of the present invention at 0.5C rate. Experiments show that the button cell has the first discharge specific capacity of 265mAh/g under the multiplying power of 0.5C, and the discharge specific capacity of 250mAh/g after the button cell is circularly charged and discharged for 250 times.
Fig. 4 is a graph showing the capacity retention rate of the full cell of example 2 of the present invention at a rate of 0.5C for 325 cycles. Experiments show that the capacity retention rate of the button cell after 325 cycles is 90% at 0.5C rate. After 300 times of cyclic charge and discharge, the specific discharge capacity is 245mAh/g, and the capacity retention rate after 300 times of cyclic charge and discharge is 90%.
Comparative example 1
The preparation method of the positive electrode slurry in example 2 was replaced with:
mixing a lithium-rich manganese-based layered material LRM, conductive carbon black SP and a binder PVDF according to a mass ratio of 8: 1: 1, uniformly mixing to obtain positive electrode slurry; the lithium-rich manganese-based layered material LRM is Li1.44Mn0.544Ni0.136Co0.136O2(ii) a The slurry viscosity of the positive electrode slurry is 6000 mPaS, and the solid content is 63%;
the remaining steps were the same as those of example 2 to obtain a button cell. The button cell prepared in comparative example 1 was subjected to a rate test, and the results are shown in fig. 2. As can be seen from fig. 2, the lithium rich material exerts a somewhat higher gram capacity in the presence of the additive and can achieve stable cycling at 10C, with comparative example 1 being able to cycle up to only 2C. Meanwhile, as can be seen from fig. 2, in the case where no additive was added, the 0.1C g capacity was 280mAh/g, the 0.2C g capacity exhibited was 265mAh/g, the 1C g capacity exhibited was 216mAh/g, and the 2C g capacity was 220 mAh/g.
Comparative example 2
Mixing a lithium-rich manganese-based layered material LRM, conductive carbon black SP, single-walled carbon nanotube SWCNT and a binder PVDF according to the mass ratio of 97.5: 0.8: 0.1: 1.5, uniformly mixing to obtain positive electrode slurry; the lithium-rich manganese-based layered material LRM is Li1.44Mn0.544Ni0.136Co0.136O2(ii) a The slurry viscosity of the positive electrode slurry was 4500mPa · S, and the solid content was 63%;
coating the positive electrode slurry on an aluminum foil with the thickness of 12 microns, coating the aluminum foil with the thickness of 240 microns, and tabletting to obtain a positive plate with the thickness of 200 microns;
silica SiO, graphite, conductive carbon black SP, single-walled carbon nanotube SWCNT and polyacrylic acid PAA are mixed according to the mass ratio of 51: 44.8: 1.04: 0.06: 3.1, uniformly mixing to obtain negative electrode slurry; in the negative electrode slurry, the gram capacity of the silicon monoxide and the graphite is 1000 mAh/g;
coating the negative electrode slurry on a copper foil with the thickness of 6 microns, coating the copper foil with the thickness of 125 microns, and tabletting to obtain a negative electrode plate with the thickness of 110 microns;
and (3) respectively assembling the negative plate, the positive plate, the Asahi formation diaphragm celgard2000 and electrolyte (the mass ratio of the additive to the lithium-rich manganese-based layered material LRM is 0.1: 97.5) to form a soft package battery and a button battery, and standing the soft package battery for 24 hours at the high temperature of 45 ℃.
The button cell prepared in comparative example 2 is subjected to rate test, and the experimental result shows that the maximum of comparative example 2 can only reach 2C cycle.
The button cell prepared in comparative example 2 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the initial specific discharge capacity was 220mAh/g at 0.5C rate, and the initial specific discharge capacity was 160mAh/g after 250 cycles of charge and discharge. After 300 times of cyclic charge and discharge, the specific discharge capacity is 100mAh/g, and the capacity retention rate after 300 times of cyclic charge and discharge is 45.45%.
Example 3
The mass ratio of the lithium-rich manganese-based layered material LRM, the additive (the additive of the lithium ion battery cathode material prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 2 is changed to 97.1: 0.5: 0.8: 0.1: 1.5 (the additive amount in the anode slurry is 0.5 wt%) to obtain an anode slurry;
the rest steps are carried out according to the steps of the example 2, and the soft package battery and the button battery are respectively assembled.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 3 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 3 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the initial specific discharge capacity was 262mAh/g at 0.5C rate, and the initial specific discharge capacity was 250mAh/g after cycling for 250 times. After 300 times of cyclic charge and discharge, the specific discharge capacity is 415mAh/g, and the capacity retention rate after 300 times of cyclic charge and discharge is 92%.
Example 4
The mass ratio of the lithium-rich manganese-based layered material LRM, the additive (the additive of the lithium ion battery cathode material prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 2 is changed to 96.6: 1: 0.8: 0.1: 1.5 (the additive amount in the anode slurry is 1wt percent) and evenly mixing to obtain anode slurry;
the rest steps are carried out according to the steps of the example 2, and the soft package battery and the button battery are respectively assembled.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 4 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 4 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 268mAh/g at 0.5C rate, and had a specific discharge capacity of 252mAh/g after 250 cycles of charge and discharge. After 300 times of cyclic charge and discharge, the specific discharge capacity is 247mAh/g, and the capacity retention rate after 300 times of cyclic charge and discharge is 94%.
Example 5
The mass ratio of the lithium-rich manganese-based layered material LRM, the additive (the additive of the lithium ion battery cathode material prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 2 is changed to 95.1: 2.5: 0.8: 0.1: 1.5 (the additive amount in the anode slurry is 2.5 wt%) to obtain an anode slurry;
the rest steps are carried out according to the steps of the example 2, and the soft package battery and the button battery are respectively assembled.
Fig. 5 is a 2000-fold SEM image of the positive electrode sheet of example 5 of the present invention, and fig. 6 is a 1000-fold SEM image of the positive electrode sheet of example 5 of the present invention. As can be seen from fig. 5 and 6, the additive of the positive electrode material of the lithium ion battery is uniformly dispersed in the gaps of the lithium-rich manganese-based layered material, so that the conductive connection is strengthened, and the ion conducting capacity of the additive is stronger, so that the multiplying power performance of the additive is improved. Due to the action of Ti-O bonds, the doping of trace titanium elements on the surface/the sub-surface is beneficial to inhibiting the formation of a disordered rock salt/spinel phase of a lithium-rich material, reducing the mismatch of interface lattices and keeping the stability of the structure to improve the rate capability and the cycle performance.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 5 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 5 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 270mAh/g at 0.5C rate and a specific discharge capacity of 262mAh/g after cyclic charge and discharge for 250 times. After 300 times of cyclic charge and discharge, the specific discharge capacity is 250mAh/g, and the capacity retention rate after 300 times of cyclic charge and discharge is 94.7%.
Example 6
The mass ratio of the lithium-rich manganese-based layered material LRM, the additive (the additive of the lithium ion battery cathode material prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 2 is changed to 92.6: 5: 0.8: 0.1: 1.5 (the additive amount in the anode slurry is 5wt percent) and evenly mixing to obtain anode slurry;
the rest steps are carried out according to the steps of the example 2, and the soft package battery and the button battery are respectively assembled.
Fig. 7 is a 10000-fold SEM image of the positive electrode sheet of example 6 of the present invention. As can be seen from FIG. 7, the additive of the lithium ion battery anode material is uniformly dispersed in the gaps of the lithium-rich manganese-based layered material, so that the conductive connection is strengthened, and the ion conducting capacity of the additive is stronger, so that the multiplying power performance of the additive is improved.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 6 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 6 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 275mAh/g at 0.5C rate and a specific discharge capacity of 250mAh/g after cyclic charging and discharging for 250 times. After 300 times of cyclic charge and discharge, the specific discharge capacity is 253mAh/g, and the capacity retention rate after 300 times of cyclic charge and discharge is 96.2%.
Example 7
The lithium-rich manganese-based layered material LRM in the positive electrode slurry in the embodiment 2 is replaced by lithium iron phosphate LFP, and the rest steps are unchanged, so that a soft package battery and a button battery are respectively assembled.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 7 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 7 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 145mAh/g at 0.5C rate and a specific discharge capacity of 146mAh/g after cyclic charge and discharge for 250 times. After 800 times of cyclic charge and discharge, the specific discharge capacity is 148mAh/g, and the capacity retention rate after 800 times of cyclic charge and discharge is 96.2%.
Example 8
The mass ratio of the lithium iron phosphate LFP, the additive (the additive of the lithium ion battery cathode material prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 7 is changed to 97.1: 0.5: 0.8: 0.1: 1.5 (the additive amount in the anode slurry is 0.5 wt%) to obtain an anode slurry;
the rest steps are carried out according to the steps of the example 2, and the soft package battery and the button battery are respectively assembled.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 8 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 8 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 150mAh/g at 0.5C rate and a specific discharge capacity of 143mAh/g after cyclic charge and discharge for 250 times. After 800 times of cyclic charge and discharge, the specific discharge capacity is 142mAh/g, and the capacity retention rate after 800 times of cyclic charge and discharge is 97.1%.
Example 9
The mass ratio of the lithium iron phosphate LFP, the additive (the additive of the lithium ion battery cathode material prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 7 is changed to 96.6: 1: 0.8: 0.1: 1.5 (the additive amount in the anode slurry is 1wt percent) and evenly mixing to obtain anode slurry;
the rest steps are carried out according to the steps of the example 2, and the soft package battery and the button battery are respectively assembled.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 9 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 9 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 155mAh/g at 0.5C rate and a specific discharge capacity of 148mAh/g after 250 cycles of charge and discharge. After 800 times of cyclic charge and discharge, the specific discharge capacity is 144mAh/g, and the capacity retention rate after 800 times of cyclic charge and discharge is 97.5%.
Example 10
The mass ratio of the lithium iron phosphate LFP, the additive (the additive of the lithium ion battery cathode material prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 7 is changed to 95.1: 2.5: 0.8: 0.1: 1.5 (the additive amount in the anode slurry is 2.5 wt%) to obtain an anode slurry;
the rest steps are carried out according to the steps of the example 2, and the soft package battery and the button battery are respectively assembled.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 10 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 10 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 157mAh/g at 0.5C rate, and had a specific discharge capacity of 148mAh/g after 250 cycles of charge and discharge. After 800 times of cyclic charge and discharge, the discharge specific capacity is 146mAh/g, and the capacity retention rate after 800 times of cyclic charge and discharge is 97.6%.
Example 11
The mass ratio of the lithium iron phosphate LFP, the additive (the additive of the lithium ion battery cathode material prepared in example 1), the conductive carbon black SP, the single-walled carbon nanotube SWCNT and the binder PVDF in example 7 is changed to 92.6: 5: 0.8: 0.1: 1.5 (the additive amount in the anode slurry is 5wt percent) and evenly mixing to obtain anode slurry;
the rest steps are carried out according to the steps of the example 2, and the soft package battery and the button battery are respectively assembled.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 11 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 11 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 158mAh/g at 0.5C rate and a specific discharge capacity of 152mAh/g after 250 cycles of charge and discharge. After 800 times of cyclic charge and discharge, the specific discharge capacity is 148mAh/g, and the capacity retention rate after 800 times of cyclic charge and discharge is 98.2%.
Example 12
The lithium-rich manganese-based layered material LRM in the positive electrode slurry in example 2 was replaced by 532-single-crystal lithium nickel manganese oxide (NCM532), and the remaining steps were unchanged, and a soft package battery and a button battery were assembled, respectively.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 12 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 12 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 170mAh/g at 0.5C rate and a specific discharge capacity of 160mAh/g after 250 cycles of charge and discharge. After 600 times of cyclic charge and discharge, the specific discharge capacity is 150mAh/g, and the capacity retention rate after 600 times of cyclic charge and discharge is 94.8%.
Example 13
The mass ratio of single-crystal 532 lithium nickel manganese oxide (NCM532), additive (additive of lithium ion battery positive electrode material prepared in example 1), conductive carbon black SP, single-wall carbon nanotube SWCNT and binder PVDF in example 12 is changed to 97.1: 0.5: 0.8: 0.1: 1.5 (the additive amount in the anode slurry is 0.5 wt%) to obtain an anode slurry;
the rest steps are carried out according to the steps of the example 2, and the soft package battery and the button battery are respectively assembled.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 13 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can achieve stable cycling at 10 ℃.
The button cell prepared in example 13 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 174mAh/g at 0.5C rate and a specific discharge capacity of 165mAh/g after 250 cycles of charge and discharge. After 600 times of cyclic charge and discharge, the specific discharge capacity is 153mAh/g, and the capacity retention rate after 600 times of cyclic charge and discharge is 95.2%.
Example 14
The mass ratio of single-crystal 532 lithium nickel manganese oxide (NCM532), additive (additive of lithium ion battery positive electrode material prepared in example 1), conductive carbon black SP, single-wall carbon nanotube SWCNT and binder PVDF in example 12 is changed to 96.6: 1: 0.8: 0.1: 1.5 (the additive amount in the anode slurry is 1wt percent) and evenly mixing to obtain anode slurry;
the rest steps are carried out according to the steps of the example 2, and the soft package battery and the button battery are respectively assembled.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 14 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 14 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 178mAh/g at 0.5C rate and a specific discharge capacity of 168mAh/g after 250 cycles of charge and discharge. After 600 times of cyclic charge and discharge, the specific discharge capacity is 152mAh/g, and the capacity retention rate after 600 times of cyclic charge and discharge is 96.2%.
Example 15
The mass ratio of single-crystal 532 lithium nickel manganese oxide (NCM532), additive (additive of lithium ion battery positive electrode material prepared in example 1), conductive carbon black SP, single-wall carbon nanotube SWCNT and binder PVDF in example 12 is changed to 95.1: 2.5: 0.8: 0.1: 1.5 (the additive amount in the anode slurry is 2.5 wt%) to obtain an anode slurry;
the rest steps are carried out according to the steps of the example 2, and the soft package battery and the button battery are respectively assembled.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 15 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 15 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 182mAh/g at 0.5C rate and a specific discharge capacity of 172mAh/g after cyclic charge and discharge for 250 times. After 600 times of cyclic charge and discharge, the specific discharge capacity is 158mAh/g, and the capacity retention rate after 600 times of cyclic charge and discharge is 96.6%.
Example 16
The mass ratio of single-crystal 532 lithium nickel manganese oxide (NCM532), additive (additive of lithium ion battery positive electrode material prepared in example 1), conductive carbon black SP, single-wall carbon nanotube SWCNT and binder PVDF in example 12 is changed to 92.6: 5: 0.8: 0.1: 1.5 (the additive amount in the anode slurry is 5wt percent) and evenly mixing to obtain anode slurry;
the rest steps are carried out according to the steps of the example 2, and the soft package battery and the button battery are respectively assembled.
The soft package battery is subjected to chemical composition and capacity operation according to the steps of the embodiment 2, and the first charge-discharge efficiency and the first medium voltage are recorded, and the experimental result shows that the discharge curves of 0.5C, 1C and 0.2C are almost overlapped, and the capacity ratio reaches 100%.
The button cell prepared in example 16 was subjected to a rate test under the same test conditions as in example 2, and the experiment shows that the button cell can realize stable cycling at 10 ℃.
The button cell prepared in example 16 was subjected to a cycle performance test under the same test conditions as in example 2, and the test showed that the button cell had a first specific discharge capacity of 185mAh/g at 0.5C rate and a specific discharge capacity of 168mAh/g after cyclic charge and discharge for 250 times. After 600 times of cyclic charge and discharge, the specific discharge capacity is 152mAh/g, and the capacity retention rate after 600 times of cyclic charge and discharge is 98.8%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a lithium ion battery positive electrode material additive comprises the following steps:
A) heating and mixing isopropyl titanate, lithium oxalate, aluminum nitrate, nano silicon dioxide, ammonium dihydrogen phosphate and water to obtain a mixed solution;
B) adjusting the pH value of the mixed solution to 9.6-10.0, and filtering and drying the obtained precipitation mixed solution;
C) grinding the dried precipitate, and burning under the condition of protective gas to obtain the lithium ion battery anode material additive with the general formula shown in the formula (1);
Li1+x+yAlxTi2-xSiyP3-yO12 (1)；
wherein 0< x <2, 0< y < 3.
2. The preparation method according to claim 1, wherein the molar ratio of isopropyl titanate, lithium oxalate, aluminum nitrate, nano-silica and ammonium dihydrogen phosphate is 0.5-1.5: 2.5-3.5: 0.5-1.5: 0.5-1.5: 4.5 to 5.5.
3. The method according to claim 1, wherein the step A) of heating and mixing isopropyl titanate, lithium oxalate, aluminum nitrate, ammonium dihydrogen phosphate and water comprises:
firstly, stirring and mixing isopropyl titanate, aluminum nitrate and part of water, then adding lithium oxalate, nano silicon dioxide, ammonium dihydrogen phosphate and the rest water, and stirring and mixing under the condition of heating;
the heating temperature is 75-85 ℃.
4. The preparation method according to claim 3, wherein the ratio of the total mass of isopropyl titanate and aluminum nitrate to the amount of part of water is 0.5-2 g: 90-110 mL;
the dosage ratio of the total mass of the lithium oxalate, the nano silicon dioxide and the ammonium dihydrogen phosphate to the rest water is 0.5-1.8 g: 40-60 mL.
5. The method according to claim 1, wherein in step B), the reagent for adjusting the pH of the mixed solution is ammonia water;
the drying temperature is 115-125 ℃, and the drying time is 22-26 h.
6. The preparation method according to claim 1, wherein in the step C), the burning temperature is 880-920 ℃, and the time is 14-18 h;
after the firing, the method further comprises the following steps: naturally cooling to room temperature, and grinding again;
the grinding frequency of the secondary grinding is 480-520 Hz, and the time is 10-14 h.
7. The additive for the positive electrode material of the lithium ion battery prepared by the preparation method of any one of claims 1 to 6.
8. A lithium ion battery positive plate is prepared by uniformly mixing raw materials including a positive material, an additive, conductive carbon black, a single-walled carbon nanotube and a binder and coating the mixture on a current collector;
the positive electrode material comprises a lithium-rich manganese-based layered material, single crystal lithium nickel manganese oxide, lithium iron phosphate or a high-voltage ternary material;
the additive is the additive for the positive electrode material of the lithium ion battery according to claim 7.
9. The positive plate of the lithium ion battery according to claim 8, wherein the mass ratio of the positive electrode material to the additive is 92-98: 0.1 to 5;
the mass ratio of the positive electrode material to the conductive carbon black to the single-walled carbon nanotube to the binder is 92-98: 0.8-1.5: 0.1-0.2: 1.5.
10. a lithium ion battery, comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the positive electrode is the positive electrode sheet of the lithium ion battery according to claim 8.
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| WO2021091387A1 (en) * | 2019-11-07 | 2021-05-14 | Technische Universiteit Delft | Solid ionic conductive additive in electrodes for lithium-ion batteries using liquid electrolyte |
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| CN103715423A (en) * | 2014-01-06 | 2014-04-09 | 深圳市贝特瑞新能源材料股份有限公司 | LiNiCoAlO2 composite cathode material and preparation method thereof, and lithium ion battery |
| WO2021091387A1 (en) * | 2019-11-07 | 2021-05-14 | Technische Universiteit Delft | Solid ionic conductive additive in electrodes for lithium-ion batteries using liquid electrolyte |
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