CN115548325B - Silicon negative electrode material and preparation method and application thereof - Google Patents
Silicon negative electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115548325B CN115548325B CN202211506599.7A CN202211506599A CN115548325B CN 115548325 B CN115548325 B CN 115548325B CN 202211506599 A CN202211506599 A CN 202211506599A CN 115548325 B CN115548325 B CN 115548325B
- Authority
- CN
- China
- Prior art keywords
- silicon
- nano
- nano silicon
- solution
- molar concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 53
- 239000010703 silicon Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000007773 negative electrode material Substances 0.000 title claims description 25
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 71
- 239000010410 layer Substances 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 43
- 230000007704 transition Effects 0.000 claims abstract description 35
- 239000010416 ion conductor Substances 0.000 claims abstract description 29
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000011247 coating layer Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 32
- 238000000576 coating method Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000010405 anode material Substances 0.000 claims description 14
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 31
- 239000003792 electrolyte Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 11
- 239000010406 cathode material Substances 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- -1 calcining Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000007599 discharging Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910000676 Si alloy Inorganic materials 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- MRVHOJHOBHYHQL-UHFFFAOYSA-M lithium metaphosphate Chemical compound [Li+].[O-]P(=O)=O MRVHOJHOBHYHQL-UHFFFAOYSA-M 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910021426 porous silicon Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 230000008719 thickening Effects 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a silicon cathode material and a preparation method and application thereof. The silicon cathode material sequentially comprises a nano silicon inner core, an inorganic fast ion conductor transition layer coated on the surface of the nano silicon inner core and a carbon coating layer positioned on the outermost layer from inside to outside, wherein the inorganic fast ion conductor comprises lithium metaaluminate. According to the invention, a lithium metaaluminate (LAO) transition layer is introduced between the nano silicon and the carbon layer, so that the effective modification of the nano silicon material is realized, the nano silicon material is prevented from being contacted with direct electrolyte, and the generation of side reaction is avoided; the volume expansion of silicon in the circulation process is inhibited from the material end, and the transition layer simultaneously serves as a buffer layer, so that the volume change is effectively relieved, the structure of the electrode material is more stable, and the electrochemical performance of the material is improved.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and relates to a silicon negative electrode material, and a preparation method and application thereof.
Background
The silicon material has the advantage of higher theoretical specific capacity as the lithium ion battery cathode, but the silicon is a semiconductor and has poor conductivity, and the volume expansion of the silicon cathode material in use causes material pulverization, thus causing the cycle life of the battery to be poor and the capacity to decay rapidly. The huge volume effect and lower conductivity limit the commercial application of silicon cathode technology. It was found that Si particles are dispersed in a matrix of carbon, and the volume change of Si during lithium intercalation and deintercalation can be absorbed by the carbon having elasticity, thereby improving the cycle performance of the electrode. However, the specific surface area of the nano-particle material is huge, side reactions with the electrolyte are increased in the circulation process, and the improvement of the electrochemical performance of the nano-particle material is limited.
The modified cladding of silicon is basically direct complex, lacks the transition layer, and the erosion of electrolyte to silicon still can't be avoided to the at utmost to solitary cladding, and along with the endless going on, the side reaction constantly takes place, worsens battery performance, is "soft" cladding simultaneously, goes to slow down the inflation of silicon, and non-initiative suppression is not obvious to the volume expansion effect.
CN104617269A discloses a silicon alloy composite negative electrode material, a preparation method and a lithium ion battery, wherein graphite and a silicon alloy coated on the surface of the graphite are used as an inner core, a shell is cracking carbon, and a nano-compounding, surface modification and coating modification technology is combined to prepare the silicon alloy composite negative electrode material with a core-shell structure. However, the composite material prepared by the method has high content of metal impurities, is easy to generate self-discharge and has poor high-temperature storage.
Therefore, how to effectively solve the problem of volume expansion of the nano silicon negative electrode material, and simultaneously avoid the corrosion of the electrolyte to silicon, and improve the electrochemical performance of the negative electrode material is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a silicon anode material and a preparation method and application thereof. According to the invention, the lithium metaaluminate (LAO) transition layer is introduced between the nano silicon and the carbon layer, so that the effective modification of the nano silicon material is realized, the nano silicon material is prevented from directly contacting with the electrolyte, and the generation of side reaction is avoided; the volume expansion of silicon in the circulation process is inhibited from the material end, and the transition layer serves as a buffer layer at the same time, so that the volume change is effectively relieved, the structure of the electrode material is more stable, and the electrochemical performance of the material is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a silicon negative electrode material, which sequentially comprises a nano silicon inner core, an inorganic fast ion conductor transition layer coated on the surface of the nano silicon inner core, and a carbon coating layer positioned on the outermost layer from inside to outside, wherein the inorganic fast ion conductor comprises lithium metaaluminate.
In the invention, the lithium metaaluminate is used as a transition layer (in-situ grown on the surface of the nano silicon), so that the nano silicon core is prevented from directly contacting with the electrolyte, and the generation of side reaction is avoided; meanwhile, the hardness of LAO is higher than that of silicon, so that the volume expansion of silicon in the circulation process is inhibited from the material end, and the transition layer serves as a buffer layer at the same time, so that the volume change is effectively relieved, and the electrode material is more stable; the LAO can also provide an effective channel for the transmission of lithium ions, reduce the impedance caused by the thickening of an SEI film in the circulation process, facilitate the de-intercalation behavior of the lithium ions and have better dynamic performance.
In the present invention, if other types of ion conductors are selected, such as aluminum metaphosphate or lithium metaphosphate, incomplete coating and structural inhomogeneity occur, because the metaphosphate itself has a flocculation effect; if a sulfide electrolyte or other oxide solid electrolyte (such as lithium lanthanum zirconium oxide) is selected, low cost, easy operation, environmental friendliness and the like cannot be realized.
In the invention, the lithium metaaluminate is a single transition layer, but is not directly mixed with the carbon layer to form a layer, and if the lithium metaaluminate is mixed with the carbon layer to form a layer as a coating layer, the transmission of ions and electrons is affected, which is not favorable for performance.
Preferably, the nano-silicon core comprises a porous nano-silicon core.
When the inner core is in a porous nano silicon structure, the volume change caused by charging and discharging can be relieved better, and the service life of the electrode material is prolonged.
Preferably, the thickness of the inorganic fast ion conductor transition layer is 1 to 5nm, such as 1nm, 2nm, 3nm, 4nm or 5nm.
In the invention, if the thickness of the transition layer of the inorganic fast ion conductor is too thin, the effects of preventing the corrosion of the electrolyte to the core porous silicon and inhibiting the volume expansion of the silicon cannot be realized, and if the thickness is too thick, the path of ion migration is increased, so that the impedance is increased, and the performance of the material is not favorably exerted.
In the present invention, the thickness of the carbon coating layer is not limited, and may be adaptively adjusted according to actual requirements, such as a desired capacitance value or other electrochemical performance requirements.
In a second aspect, the present invention provides a method for preparing a silicon anode material according to the first aspect, the method comprising the steps of:
and mixing a lithium salt solution, an organic aluminum solution and the nano-silicon particles to obtain sol-gel coated with the nano-silicon particles, calcining, and coating with carbon to obtain the silicon negative electrode material.
According to the preparation method provided by the invention, the in-situ coating of the inorganic fast ion conductor (lithium metaaluminate) transition layer on the nano silicon particles is realized through a sol-gel method, compared with pure physical mixed coating, the uniformity and consistency of a coating layer are more facilitated, the gamma crystal form lithium metaaluminate can be obtained only by adopting the sol-gel method, the crystal form cannot be obtained by adopting a common solid phase method, and the uniform in-situ coating is difficult to realize by adopting the common solid phase method for sintering, so that the compact structure cannot be obtained, a buffer layer of electrolyte can be directly isolated, the carbon coating is further realized, and the conductivity of the material is improved; the preparation method provided by the invention has the advantages of simple process and low cost, greatly improves the production efficiency of the cathode material, can better meet the requirement of industrial production, realizes large-scale production, and has great application prospect.
Preferably, the lithium salt solution comprises a lithium acetate solution and/or a lithium carbonate solution, preferably a lithium acetate solution.
In the invention, lithium acetate is used as a reaction raw material, so that the lithium salt can be completely dissolved better, and the subsequent high-temperature calcination gas production phenomenon is avoided.
Preferably, the molar concentration of the lithium salt solution is 1.5 to 2mol/L, such as 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L or 2mol/L.
Preferably, the solvent in the lithium salt solution includes absolute ethanol.
Preferably, the D50 of the nano-silicon particles is 10 to 100nm, such as 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm or 100nm and the like.
In the invention, the D50 of the nano silicon particles is too small, which causes difficult dispersion and easy agglomeration, thus causing nonuniform coating, while the D50 is too large, which affects the service life, multiplying power and cycle performance of the material.
Preferably, the molar concentration of the organoaluminum in the mixed solution of the organoaluminum solution and the silicon nanoparticles is 0.3 to 0.6mol/L, for example, 0.3mol/L, 0.4mol/L, 0.5mol/L, or 0.6 mol/L.
Preferably, in the mixed solution of the organic aluminum solution and the nano silicon particles, the molar concentration of the nano silicon particles is 1 to 1.2mol/L, such as 1mol/L, 1.03mol/L, 1.05mol/L, 1.08mol/L, 1.1mol/L, 1.13mol/L, 1.15mol/L, 1.18mol/L or 1.2mol/L.
Preferably, the organoaluminum in the organoaluminum solution comprises aluminum isopropoxide.
Preferably, the solvent in the organoaluminum solution comprises anhydrous ethanol.
Preferably, the nano-silicon particles comprise porous nano-silicon particles.
In the invention, the preparation method of the porous nano silicon particles is a method for obtaining the porous nano silicon material by conventional technical means, the invention is applicable, and exemplarily, the invention provides a preparation method of the porous nano silicon particles, which comprises the following steps:
soaking silicon alloy (aluminum-silicon alloy, magnesium-silicon alloy and the like) in a hydrochloric acid solution with the mass concentration of 5-15% to obtain the porous nano silicon particles.
Preferably, the method of mixing comprises stirring to obtain a sol-gel state.
Preferably, after the mixing, drying is also included.
Preferably, the temperature of the calcination is 500 to 700 ℃, for example, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃ or the like.
In the invention, the calcination temperature is too low to obtain the lithium metaaluminate with the target crystal form, and the calcination temperature is too high to cause the loss of lithium salt to be increased, the crystal form of the lithium metaaluminate to be changed and the generation of impurity phases.
Preferably, the calcination time is 3 to 6h, such as 3h, 4h, 5h or 6h.
Preferably, the carbon coating comprises any one of gas phase carbon coating, liquid phase carbon coating or solid phase carbon coating or a combination of at least two of the above.
In the invention, the preparation process of the carbon coating is a conventional preparation process, and comprises the selection of a carbon source and the carbonization temperature, namely, the invention is applicable to the carbon coating process as long as a carbon layer can be obtained.
As a preferable technical scheme, the preparation method comprises the following steps:
stirring a lithium salt solution with the molar concentration of 1.5 to 2mol/L, an aluminum isopropoxide solution and the nano-silicon particles to obtain a sol-gel coated with the nano-silicon particles, drying, calcining at 500 to 700 ℃ for 3 to 6 hours, and coating with gas phase carbon to obtain the silicon anode material;
wherein in the mixed solution of the aluminum isopropoxide solution and the nano silicon particles, the molar concentration of aluminum isopropoxide is 0.3 to 0.6mol/L, and the molar concentration of the nano silicon particles is 1 to 1.2mol/L.
In a third aspect, the present invention also provides a lithium ion battery, which includes the silicon negative electrode material according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the lithium metaaluminate (LAO) transition layer is introduced between the nano silicon and the carbon layer, so that the effective modification of the nano silicon material is realized, the nano silicon material is prevented from contacting with direct electrolyte, and the generation of side reaction is avoided; the volume expansion of silicon in the circulation process is inhibited from the material end, and the transition layer simultaneously serves as a buffer layer, so that the volume change is effectively relieved, the structure of the electrode material is more stable, and the electrochemical performance of the material is improved. When the battery adopts the cathode material provided by the invention, the rate capability can reach more than 90.9%; the capacity retention rate after 300 cycles under 0.1A/g can reach more than 87.5%.
(2) The preparation method provided by the invention has the advantages of simple process and low cost, greatly improves the production efficiency of the cathode material, can better meet the requirement of industrial production, realizes large-scale production, and has great application prospect.
Drawings
Fig. 1 is a schematic flow diagram of the preparation method provided in example 1.
Fig. 2 is an XRD pattern of the silicon anode material provided in example 1.
Fig. 3 is an SEM image of the silicon anode material provided in example 1.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a silicon cathode material, which sequentially comprises a nano-silicon core, an inorganic fast ion conductor transition layer coated on the surface of the nano-silicon core and a carbon coating layer positioned on the outermost layer from inside to outside, wherein the inorganic fast ion conductor is lithium metaaluminate, and the thickness of the inorganic fast ion conductor transition layer is 3.5nm.
The preparation method of the silicon negative electrode material comprises the following steps (the flow is shown in figure 1):
1) Firstly, taking 20mL of absolute ethyl alcohol and 10mL of deionized water by using a measuring cylinder, pouring the absolute ethyl alcohol and the deionized water into a beaker, uniformly stirring and mixing, adding 3.30g (0.05 mol) of lithium acetate into a mixed solvent while stirring, and continuously stirring until the lithium acetate is completely dissolved to obtain a colorless transparent solution A (1.67 mol/L);
weighing 100mL of absolute ethanol, pouring into a beaker, weighing 10.22g of isopropanol aluminum powder, stirring and adding into the beaker to uniformly disperse the isopropanol aluminum in the ethanol, and then adding 2.80g of porous nano silicon particles (D50 is 50 nm) to obtain a colorless transparent solution B (the molar concentration of the isopropanol aluminum is 0.5mol/L, and the molar concentration of the porous nano silicon particles is 1 mol/L);
2) Adding the solution A into the solution B, continuously stirring for 2h, then transferring the mixed solution into a water bath kettle at 60 ℃ to be dried by distillation (in a solvent gel state), and then drying in a drying oven at constant temperature overnight;
3) Crushing, putting a sample into a muffle furnace, calcining at 600 ℃ for 5h, and carrying out carbon coating on the calcined material by using a CVD (chemical vapor deposition) method to obtain the silicon negative electrode material.
Fig. 2 shows an XRD pattern of the silicon anode material provided in example 1, and fig. 3 shows an SEM pattern of the silicon anode material provided in example 1, and it can be seen from fig. 2 that when the calcination temperature is 600 ℃, the peak shape of the obtained material is sharp, the degree of crystallization is good, and the obtained material is an ideal target.
Fig. 3 shows an SEM image of the silicon anode material provided in example 1, as can be seen from fig. 3, the silicon core is continuously and uniformly covered by the lithium metaaluminate transition layer, and an ideal carbon @ lao @ silicon structure target is obtained, i.e., the outermost light layer is a carbon layer, the middle dark gray layer is the lithium metaaluminate transition layer, and the inner black layer is the silicon core.
Example 2
The embodiment provides a silicon anode material, which sequentially comprises a nano silicon core, an inorganic fast ion conductor transition layer coated on the surface of the nano silicon core and a carbon coating layer positioned on the outermost layer from inside to outside, wherein the inorganic fast ion conductor is lithium metaaluminate, and the thickness of the inorganic fast ion conductor transition layer is 5nm.
The preparation method of the silicon negative electrode material comprises the following steps:
1) Firstly, taking 20mL of absolute ethyl alcohol and 10mL of deionized water by using a measuring cylinder, pouring the absolute ethyl alcohol and the deionized water into a beaker, uniformly stirring and mixing, adding 3.96g (0.06 mol) of lithium acetate into a mixed solvent while stirring, and continuously stirring until the lithium acetate is completely dissolved to obtain a colorless transparent solution A (2 mol/L);
weighing 100mL of absolute ethanol, pouring the absolute ethanol into a beaker, weighing 12.24g of isopropanol aluminum powder, stirring and adding the isopropanol aluminum powder into the beaker to uniformly disperse the isopropanol aluminum in the ethanol, and then adding 3.22g of porous nano silicon particles (D50 is 100 nm) to obtain a colorless transparent solution B (the molar concentration of the isopropanol aluminum is 0.6mol/L, and the molar concentration of the porous nano silicon particles is 1.15 mol/L);
2) Adding the solution A into the solution B, continuously stirring for 2h, transferring the mixed solution into a water bath kettle at 60 ℃ to be dried by distillation (in a solvent gel state), drying at constant temperature in a drying oven overnight,
3) And crushing, putting the sample into a muffle furnace, calcining at 550 ℃ for 5 hours at constant temperature, and carrying out carbon coating on the calcined material by using a CVD (chemical vapor deposition) method to obtain the silicon negative electrode material.
Example 3
The embodiment provides a silicon anode material, which sequentially comprises a nano silicon core, an inorganic fast ion conductor transition layer coated on the surface of the nano silicon core and a carbon coating layer positioned on the outermost layer from inside to outside, wherein the inorganic fast ion conductor is lithium metaaluminate, and the thickness of the inorganic fast ion conductor transition layer is 1nm.
The preparation method of the silicon negative electrode material comprises the following steps:
1) Firstly, taking 20mL of absolute ethyl alcohol and 10mL of deionized water by using a measuring cylinder, pouring the absolute ethyl alcohol and the deionized water into a beaker, uniformly stirring and mixing, adding 2.97g (0.045 mol) of lithium acetate into a mixed solvent while stirring, and continuously stirring until the lithium acetate is completely dissolved to obtain a colorless transparent solution A (1.5 mol/L);
weighing 100mL of absolute ethanol, pouring the absolute ethanol into a beaker, weighing 6.12g of isopropanol aluminum powder, stirring and adding the isopropanol aluminum powder into the beaker to uniformly disperse the isopropanol aluminum in the ethanol, and then adding 3.08g of porous nano silicon particles (D50 is 80 nm) to obtain a colorless transparent solution B (the molar concentration of the isopropanol aluminum is 0.3mol/L, and the molar concentration of the porous nano silicon particles is 1.1 mol/L);
2) Adding the solution A into the solution B, continuously stirring for 2h, transferring the mixed solution into a water bath kettle at 60 ℃ to be dried by distillation (in a solvent gel state), drying at constant temperature in a drying oven overnight,
3) Crushing, putting a sample into a muffle furnace, carrying out constant temperature calcination treatment at 600 ℃ for 3h, and carrying out carbon coating on the calcined material by using a CVD (chemical vapor deposition) method to obtain the silicon cathode material.
Example 4
This example differs from example 1 in that the calcination temperature in step 3) of this example is 500 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Example 5
The difference between this example and example 1 is that the calcination temperature in step 3) of this example is 700 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Example 6
This example differs from example 1 in that the calcination temperature in step 3) of this example is 450 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Example 7
This example differs from example 1 in that the calcination temperature in step 3) of this example is 800 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Example 8
The difference between this example and example 1 is that the thickness of the transition layer of the inorganic fast ion conductor in this example is 6nm, and the calcination time in step 3) in the preparation method is 6h.
The remaining preparation methods and parameters were in accordance with example 1.
Example 9
The present embodiment is different from embodiment 1 in that the silicon particles in the present embodiment are non-porous nano silicon particles.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The difference between the comparative example and the example 1 is that the silicon anode material provided by the comparative example is not provided with an inorganic fast ion conductor transition layer, and in the preparation method, the porous nano silicon particles are directly subjected to carbon coating.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 2
The difference between the comparative example and the example 1 is that the silicon negative electrode material provided by the comparative example is not provided with a carbon coating layer, and the preparation method does not carry out a carbon coating process.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 3
The difference between the comparative example and the example 1 is that, in the silicon negative electrode material provided by the comparative example, the inorganic fast ion conductor transition layer is not arranged, but lithium metaaluminate is mixed and doped in the carbon coating process, namely, the surface of the silicon core is directly coated with a coating layer formed by mixing carbon and lithium metaaluminate (the mass ratio of the lithium metaaluminate in the coating layer is 1.0%).
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 4
The difference between this comparative example and example 1 is that in this comparative example, the inorganic fast ion conductor is lithium metaphosphate, the raw material of lithium metaphosphate and the preparation process in the preparation method refer to the method provided in CN109941981A, and the order of addition of silicon is the same as in example 1.
The rest of the process was identical to example 1.
The silicon negative electrode materials provided in examples 1 to 7 and comparative examples 1 to 4 were used as negative electrode active materials to prepare negative electrode sheets, and the button cells were obtained using lithium sheets as counter electrodes.
Electrochemical performance tests were performed on the batteries provided in examples 1 to 9 and comparative examples 1 to 4, and the results are shown in table 1.
1. And (3) multiplying power testing: the batteries provided in examples and comparative examples were tested in the order of steps (1) to (6):
(1) Charging to 3.0V at a current density of 0.1A/g; discharging to 0.01V at a current density of 0.1A/g for 1 cycle, and performing 5 cycles;
(2) Charging to 3.0V at a current density of 0.2A/g; discharging to 0.01V at a current density of 0.2A/g for 1 cycle, and performing 5 cycles;
(3) Charging to 3.0V at a current density of 0.4A/g; discharging to 0.01V at a current density of 0.4A/g for 1 cycle, and performing 5 cycles;
(4) Charging to 3.0V at a current density of 0.8A/g; discharging to 0.01V at a current density of 0.8A/g for 1 cycle, and performing 5 cycles;
(5) Charging to 3.0V at a current density of 1.6A/g; discharging to 0.01V at a current density of 1.6A/g for 1 cycle, and performing 5 cycles;
(6) Charging to 3.0V at a current density of 0.1A/g; discharging to 0.01V at a current density of 0.1A/g for 1 cycle, and performing 5 cycles;
rate capability: the ratio of the corresponding battery capacity after the discharge in the step (6) to the corresponding battery capacity after the discharge in the step (1);
2. and (3) cycle testing: charging to 3.0V at a current density of 0.1A/g; then, the current density was 0.1A/g, and the discharge was carried out to 0.01V, which was regarded as 1 cycle, and 300 cycles were carried out in total. The retention of the battery capacity after 300 cycles was calculated.
TABLE 1
From the data results of the examples 1 and 6 to 7, it is known that too low calcination temperature results in low synthesis quality of gamma-type lithium metaaluminate, an effective coating layer cannot be formed, corrosion of electrolyte and acceleration of ion transmission cannot be avoided, and too high calcination temperature affects excessive volatilization of lithium salt in the synthesis process, generates various impurity phases, and hinders performance of the battery material.
From the data results of example 1 and example 8, it can be seen that the thickness of the transition layer of the inorganic fast ion conductor is too thick, which is not good for the transmission of ions, and results in the decrease of the dynamic and cycling performance of the battery.
From the data results of example 1 and example 9, it is known that the porous silicon core can better reduce the swelling effect of the cell itself and improve the electrical properties.
From the data results of example 1 and comparative examples 1-2, it is clear that in the silicon negative electrode material, the transition layer and the carbon coating layer are absent, and the transition layer and the carbon coating layer can act synergistically to realize excellent electrical properties of the battery.
From the data results of example 1 and comparative example 3, it is understood that the direct mixed coating of carbon and lithium metaaluminate cannot achieve the improvement of the battery material dynamics and deteriorates the cycle to some extent.
From the data results of example 1 and comparative example 4, it is known that the use of other ion conductors is not favorable for uniform formation of the coating layer, and corrosion of the electrolyte to the silicon core cannot be effectively inhibited, resulting in a decrease in cycle performance.
In conclusion, the inorganic fast ion conductor transition layer is coated on the surface of the nano silicon core in situ, and simultaneously, the inorganic fast ion conductor transition layer and the carbon coating layer on the outermost layer act synergistically, so that the effective modification of the nano silicon material is realized, the nano silicon material is prevented from being contacted with direct electrolyte, and the generation of side reactions is avoided; the volume expansion of silicon in the circulation process is inhibited from the material end, and the transition layer simultaneously serves as a buffer layer, so that the volume change is effectively relieved, the structure of the electrode material is more stable, and the electrochemical performance of the material is improved. When the battery adopts the cathode material provided by the invention, the rate capability can reach more than 90.9%; the capacity retention rate after 300 cycles under 0.1A.g can reach more than 87.5%.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (4)
1. A silicon negative electrode material is characterized by comprising a nano silicon inner core, an inorganic fast ion conductor transition layer coated on the surface of the nano silicon inner core and a carbon coating layer positioned on the outermost layer in sequence from inside to outside, wherein the inorganic fast ion conductor is lithium metaaluminate; the lithium metaaluminate is gamma-crystal lithium metaaluminate; the inorganic fast ion conductor transition layer is coated on the surface of the nano silicon inner core in situ; the nano-silicon core comprises a porous nano-silicon core; the thickness of the inorganic fast ion conductor transition layer is 1 to 5nm;
the silicon negative electrode material is prepared by the following preparation method, and the preparation method comprises the following steps:
stirring a lithium acetate solution with the molar concentration of 1.5 to 2mol/L, an aluminum isopropoxide solution and nano silicon particles with the D50 of 10 to 100nm to obtain sol gel for coating the nano silicon particles, drying, calcining at 500 to 700 ℃, and coating with carbon to obtain the silicon negative electrode material;
wherein in the mixed solution of the aluminum isopropoxide solution and the nano silicon particles, the molar concentration of aluminum isopropoxide is 0.3 to 0.6mol/L, and the molar concentration of the nano silicon particles is 1 to 1.2mol/L.
2. A method for preparing a silicon anode material according to claim 1, comprising the steps of:
stirring a lithium acetate solution with the molar concentration of 1.5 to 2mol/L, an aluminum isopropoxide solution and nano silicon particles with the D50 of 10 to 100nm to obtain sol gel for coating the nano silicon particles, drying, calcining at 500 to 700 ℃, and coating with carbon to obtain the silicon negative electrode material;
wherein in the mixed solution of the aluminum isopropoxide solution and the nano silicon particles, the molar concentration of aluminum isopropoxide is 0.3 to 0.6mol/L, and the molar concentration of the nano silicon particles is 1 to 1.2mol/L.
3. The method for preparing the silicon anode material according to claim 2, wherein the method comprises the steps of:
stirring a lithium salt solution with the molar concentration of 1.5 to 2mol/L, an aluminum isopropoxide solution and the nano-silicon particles to obtain a sol-gel coated with the nano-silicon particles, drying, calcining at 500 to 700 ℃ for 3 to 6 hours, and coating with gas phase carbon to obtain the silicon anode material;
wherein in the mixed solution of the aluminum isopropoxide solution and the nano silicon particles, the molar concentration of aluminum isopropoxide is 0.3 to 0.6mol/L, and the molar concentration of the nano silicon particles is 1 to 1.2mol/L.
4. A secondary battery comprising the silicon negative electrode material according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211506599.7A CN115548325B (en) | 2022-11-29 | 2022-11-29 | Silicon negative electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211506599.7A CN115548325B (en) | 2022-11-29 | 2022-11-29 | Silicon negative electrode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115548325A CN115548325A (en) | 2022-12-30 |
| CN115548325B true CN115548325B (en) | 2023-03-14 |
Family
ID=84722427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211506599.7A Active CN115548325B (en) | 2022-11-29 | 2022-11-29 | Silicon negative electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115548325B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116207241B (en) * | 2023-05-06 | 2023-07-25 | 江苏正力新能电池技术有限公司 | Negative electrode material, preparation method thereof, negative electrode and lithium ion battery |
| CN117352704B (en) * | 2023-11-30 | 2024-06-25 | 瑞浦兰钧能源股份有限公司 | Silicon anode material and preparation method and application thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8753545B2 (en) * | 2010-03-03 | 2014-06-17 | 3M Innovative Properties Company | Composite negative electrode materials |
| CN103682334B (en) * | 2013-12-04 | 2015-10-28 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method of the lithium manganese silicate anode material that a kind of nano zine oxide is coated |
| CN104617269B (en) * | 2015-01-23 | 2018-03-13 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of silicon alloy composite negative pole material, preparation method and lithium ion battery |
| CN108134051B (en) * | 2016-12-01 | 2023-06-06 | 内蒙古欣源石墨烯科技股份有限公司 | Silicon-carbon composite anode material and preparation method thereof |
| US11362327B2 (en) * | 2017-09-05 | 2022-06-14 | Institute Of Physics, Chinese Academy Of Sciences | Double layer-coated nano-silicon negative electrode material, a method for preparing the same and use thereof |
| CN109941981B (en) * | 2019-03-15 | 2020-10-27 | 江西赣锋锂业股份有限公司 | Method for preparing high-purity lithium metaphosphate |
| CN111048756A (en) * | 2019-12-04 | 2020-04-21 | 兰溪致德新能源材料有限公司 | High-conductivity silica negative electrode material and application thereof |
| CN113410442A (en) * | 2021-06-09 | 2021-09-17 | 恒大新能源技术(深圳)有限公司 | Silicon-based negative electrode material and preparation method thereof, negative plate and secondary battery |
| CN113270586B (en) * | 2021-07-19 | 2021-09-28 | 北京壹金新能源科技有限公司 | Preparation and application of in-situ polymerization coated modified silicon-based negative electrode material |
| CN114497522A (en) * | 2022-04-01 | 2022-05-13 | 深圳索理德新材料科技有限公司 | Silica composite negative electrode material of lithium ion battery and preparation method of silica composite negative electrode material |
-
2022
- 2022-11-29 CN CN202211506599.7A patent/CN115548325B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115548325A (en) | 2022-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111628155B (en) | Molybdenum-tin bimetallic sulfide as negative electrode material of lithium ion/sodium ion battery and preparation method thereof | |
| CN115548325B (en) | Silicon negative electrode material and preparation method and application thereof | |
| CN112289998B (en) | Ternary cathode material with double-layer coating structure on surface and preparation method thereof | |
| CN109119621B (en) | Lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material and preparation method thereof | |
| CN116177525B (en) | Soft carbon coated spherical lignin carbon material, preparation method thereof and application thereof in sodium ion battery anode material | |
| CN114094067A (en) | Ternary positive electrode material, preparation method and application thereof | |
| CN108598458B (en) | Nitrogen-doped lithium titanate composite material, preparation method thereof and lithium ion battery | |
| CN117154012A (en) | Sulfide all-solid-state battery and preparation method thereof | |
| CN114512665B (en) | Preparation method of metal ion doped sodium ion battery negative plate | |
| CN108539136B (en) | Preparation method of stannous sulfide/nitrogen-doped carbon composite flower ball and application of stannous sulfide/nitrogen-doped carbon composite flower ball in negative electrode of lithium ion battery | |
| CN114975964A (en) | Polypyrrole-coated tin dioxide/nano carbon sphere negative electrode material, preparation method thereof and sodium ion battery | |
| CN114349051A (en) | Multi-metal molybdate, preparation method thereof and lithium ion battery | |
| CN111146443A (en) | Zinc electrode material for zinc battery and preparation method thereof | |
| CN114944288B (en) | Flower-like bismuth trioxide, preparation method and application thereof, and prepared electrode | |
| CN114188521B (en) | Light coating layer on surface of graphite anode material of double-ion battery and preparation method | |
| CN114050245B (en) | Composite positive electrode material with spring-like lamellar structure, and preparation method and application thereof | |
| CN116864651A (en) | O3-type nickel-iron-manganese-based low-nickel monocrystal positive electrode material and preparation method and application thereof | |
| CN115196682A (en) | Method for improving cycle life of lithium manganate | |
| CN116230879A (en) | Positive electrode material, preparation method thereof and lithium ion battery | |
| CN114583121A (en) | Anion-doped modified lithium ion battery positive electrode material and preparation method and application thereof | |
| CN111653765A (en) | Preparation method of niobium-doped nickel-cobalt lithium aluminate anode material | |
| CN110707304A (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN112624087B (en) | Aluminum ion battery positive electrode material prepared from hydrogenated fullerene material, and preparation and application thereof | |
| CN118183696B (en) | Hard carbon negative electrode material, preparation method thereof and battery | |
| JP2020047383A (en) | Positive electrode active material, method for manufacturing the same, positive electrode and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 40077989 Country of ref document: HK |