CN110034283A - Tin phosphide composite material and preparation method and application thereof - Google Patents
Tin phosphide composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN110034283A CN110034283A CN201811080354.6A CN201811080354A CN110034283A CN 110034283 A CN110034283 A CN 110034283A CN 201811080354 A CN201811080354 A CN 201811080354A CN 110034283 A CN110034283 A CN 110034283A
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- Prior art keywords
- tin
- composite material
- phosphatization
- carbon
- hollow
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 158
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 77
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000463 material Substances 0.000 claims abstract description 71
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 239000007773 negative electrode material Substances 0.000 claims description 17
- 229910001415 sodium ion Inorganic materials 0.000 claims description 17
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 229910001887 tin oxide Inorganic materials 0.000 claims description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 2
- 229940079864 sodium stannate Drugs 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract 2
- 239000010410 layer Substances 0.000 abstract 2
- 239000006182 cathode active material Substances 0.000 abstract 1
- 229910052718 tin Inorganic materials 0.000 description 109
- 229910052744 lithium Inorganic materials 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009432 framing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VRVAZSINCAZFLH-UHFFFAOYSA-N oxygen(2-) tin(4+) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Sn+4] VRVAZSINCAZFLH-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910020462 K2SnO3 Inorganic materials 0.000 description 1
- 229910004751 Na15Sn4 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NQXGLOVMOABDLI-UHFFFAOYSA-N sodium oxido(oxo)phosphanium Chemical compound [Na+].[O-][PH+]=O NQXGLOVMOABDLI-UHFFFAOYSA-N 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- H01M10/052—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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/387—Tin or alloys based on tin
-
- 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
- H01M4/5805—Phosphides
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a tin phosphide composite material and a preparation method and application thereof. The preparation method comprises the following steps: carrying out hydrothermal reaction on a tin source material and a carbon source material under an alkaline condition to obtain a hollow tin dioxide ball with a carbon source attached to the surface; carrying out carbonization treatment on tin dioxide in an inert atmosphere to obtain a hollow tin dioxide ball with a surface coated with a carbon layer; and (3) heating the hollow tin dioxide ball coated with the carbon layer on the surface and a phosphorus source material in an inert atmosphere to react to obtain the composite material containing the tin phosphide, the hollow tin dioxide and carbon, wherein the carbon is the coating layer. The material obtained by the preparation method of the tin phosphide composite material comprises tin phosphide, hollow tin dioxide and carbon, and the carbon is a coating layer, so that the tin phosphide composite material has good conductivity, can effectively inhibit the volume expansion effect when being used as a battery cathode active material, and improves the electrochemical performance of a battery.
Description
Technical field
The invention belongs to phosphorization tin field of material technology, and in particular to a kind of phosphorization tin composite material and preparation method and
Using.
Background technique
As PC, video camera, mobile phone step on the high speed development and electric vehicle, hybrid vehicle of mobile device
Fast development, the demand of energy storage device is also in substantial increase.Secondary cell due to having a characteristic of recyclable charge and discharge and
As the main flow direction of mobile energy storage device, and main secondary cell is lithium ion battery at present, in lithium ion battery just,
The material of cathode is the core component of battery, and performance directly determines the chemical property of battery, therefore constantly research and development
Have excellent performance, cheap positive electrode, negative electrode material have become the emphasis of battery material, be formed to two so far
Member, ternary material are positive electrode, using carbon-based material, silica-base material, Si-C composite material as the pattern of negative electrode material, but still
Further research and development are so needed to be suitable for the positive and negative pole material of new situations demand.
Research shows that the capacity of tin is 847mAhg in storage sodium material-1, the capacity of phosphorus is 2596mAhg-1, change
Close object phosphorization tin (Sn4P3) and sodium generation electrochemical reaction generation Na15Sn4And Na3P, therefore using phosphorization tin as sodium electricity cathode material
When material, volume and capacity ratio is up to 6650mAhcm-3.There is so high volume and capacity ratio in view of phosphorization tin, it may be considered that by it
As sodium-ion battery, the negative electrode active material of lithium ion battery.But the synthetic method of phosphorization tin mostly uses high energy ball at present
Mill method or hydro-thermal reaction method, as the Chinese patent of Publication No. CN105006551A is disclosed metallic tin powder, phosphorus part and mill
Ball is added in the ball grinder of high energy ball mill, under inert gas or nitrogen protection, is carried out ball milling and is chemically reacted simultaneously,
Obtain a nanometer phosphatization tin particles.For another example the Chinese patent of Publication No. CN106450306A discloses a kind of Sn4P3Sodium-ion battery is negative
The preparation method of pole material specifically includes (1) for red phosphorus and carries out ball-milling treatment；(2) Sn salt is dissolved in solvent, prepares Sn salt
Dispersion liquid；(3) red phosphorus after the Sn salt dispersion liquid and ball milling is mixed, is got a uniform mixture；It (4) will be described
Mixed solution is transferred in reaction kettle, and reaction obtains suspension；(5) sediment is obtained by filtration in the suspension, it will be described heavy
Starch is washed, dry, obtains Sn4P3Anode material of lithium-ion battery.In addition, it has been reported that can be using sodium hypophosphite also
The method of former stannic oxide prepares Sn4P3.But the Sn prepared in these existing reports4P3It is undefined structure or solid
Nanometer spherical structure.Due to Sn4P3During circulating battery, there are Volumetric expansion, up to 400% volume change is had
Change, therefore, the Sn of solid construction4P3The problem of as structure crushing is easy to appear in the long-term circulation of negative electrode material in the battery,
In addition, the problems such as there is also poorly conductives.
Summary of the invention
For current phosphorization tin synthetic method synthesis phosphorization tin as cell negative electrode material when there are volume expansion greatly, lead
The problems such as electrically poor, the present invention provides a kind of phosphorization tin composite material and preparation method.
Further, the application that the present invention also provides it in multiple fields.
For achieving the above object, technical scheme is as follows:
A kind of preparation method of phosphatization tin composite material, at least includes the following steps:
Tin source material, carbon source material are mixed to and maintain to carry out under alkaline condition hydro-thermal reaction, surface is obtained and is attached with
The hollow stannic oxide ball of carbon source；
Under an inert atmosphere, carbonization treatment is carried out to the hollow stannic oxide ball of acquisition, obtains coated with carbon bed
Hollow stannic oxide ball；
Surface is coated with the hollow stannic oxide ball of carbon-coating and phosphorus source material carries out mixing treatment, and in inert atmosphere
Heating makes the two react, and obtains phosphatization tin composite material；
The phosphatization tin composite material at least contains phosphorization tin, hollow stannic oxide and carbon, and the carbon coating is in the phosphorus
Change the surface of tin, hollow stannic oxide.
Correspondingly, a kind of phosphatization tin composite material, the phosphatization tin composite material at least contain phosphorization tin, hollow titanium dioxide
Tin and carbon, the carbon coating is in the surface of phosphorization tin, hollow stannic oxide.
And a kind of lithium ion battery or sodium-ion battery negative electrode tab, including negative electrode active material, the negative electrode active material
Material is phosphatization tin composite material, and the phosphatization tin composite material at least contains phosphorization tin, hollow stannic oxide and carbon, the carbon packet
It is overlying on the surface of phosphorization tin, hollow stannic oxide.
And correspondingly, a kind of lithium ion battery or sodium-ion battery, including negative electrode tab, the negative electrode tab contain phosphatization
Tin composite material, the phosphatization tin composite material at least contain phosphorization tin, hollow stannic oxide and carbon, and the carbon coating is in phosphatization
The surface of tin, hollow stannic oxide.
The invention has the benefit that
Compared with the existing technology, the preparation method of phosphatization tin composite material of the present invention, using tin source material combination carbon source material
The hollow stannic oxide ball that surface is attached with carbon source is prepared by hydro-thermal reaction in material, is then carbonized to carbon source, and with
The reaction of phosphorus source material generates hydrogen phosphide, restores hollow stannic oxide by hydrogen phosphide, generates phosphorization tin, and maintain original
There is the structural framing of hollow stannic oxide, can be effectively suppressed when so that the phosphatization tin composite material obtained is as cell negative electrode material
Volume expansion, and have good electric conductivity；In addition, this preparation method condition is simple, the requirement to equipment is low, is suitble to extensive
Production.
Phosphatization tin composite material provided by the invention, due to simultaneously including phosphorization tin, hollow stannic oxide and carbon, and carbon
It is coated on the surface of phosphorization tin, hollow stannic oxide, so that phosphatization tin composite material has good electric conductivity, as battery
It when negative electrode active material, can effectively inhibit Volumetric expansion, improve the chemical property of battery.
Anode plate for lithium ionic cell or sodium-ion battery negative electrode tab provided by the invention, since negative electrode active material is using packet
Phosphatization tin composite material containing phosphorization tin, hollow stannic oxide and carbon, so that negative electrode tab has good conductive property and antibody
Product expansion effect, the problems such as being able to solve crushing that negative electrode tab occurs in battery charging and discharging cyclic process, fall off.
Lithium ion battery or sodium-ion battery provided by the invention, due to containing phosphatization tin composite material in negative electrode tab, and
And contain phosphorization tin, hollow stannic oxide and carbon in phosphatization tin composite material, and carbon coating is in phosphorization tin, hollow stannic oxide
Surface so that lithium ion battery or sodium-ion battery have good electric conductivity, while can effectively inhibit charge and discharge process
In volume expansion so that lithium ion battery or sodium-ion battery have good chemical property.
Detailed description of the invention
It, below will be to needed in the embodiment attached to be illustrated more clearly that the technical solution in the embodiment of the present invention
Figure is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this field
For those of ordinary skill, without creative efforts, it is also possible to obtain other drawings based on these drawings.
Fig. 1 is the SEM figure of phosphatization tin composite material prepared by the embodiment of the present invention 1；
Fig. 2 is the XRD diagram of phosphatization tin composite material prepared by the embodiment of the present invention 1；
Fig. 3 is that phosphatization tin composite material prepared by the embodiment of the present invention 1 is made lithium-ion negative pole piece and is assembled into half-cell
When cyclic voltammetry curve；
Fig. 4 is that phosphatization tin composite material prepared by the embodiment of the present invention 1 is made anode plate for lithium ionic cell and is assembled into half
The AC impedance curve of battery；
Fig. 5 is that phosphatization tin composite material prepared by the embodiment of the present invention 1 is made anode plate for lithium ionic cell and is assembled into
Cyclic curve of the half-cell under different multiplying；
Fig. 6 is that phosphatization tin composite material prepared by the embodiment of the present invention 1 is made anode plate for lithium ionic cell and is assembled into
The cyclic curve of half-cell；
Fig. 7 is the XRD diagram of phosphatization tin composite material prepared by the embodiment of the present invention 2；
Fig. 8 is the SEM figure of phosphatization tin composite material prepared by the embodiment of the present invention 2；
Fig. 9 is the element EDS map in the embodiment of the present invention 2 in Fig. 7 boxed area；
Figure 10 is that phosphatization tin composite material prepared by the embodiment of the present invention 2 is made anode plate for lithium ionic cell and is assembled into
The cyclic curve of half-cell；
Figure 11 is that phosphatization tin composite material prepared by the embodiment of the present invention 2 is made anode plate for lithium ionic cell and is assembled into
Cyclic curve of the half-cell under different multiplying.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, with reference to the accompanying drawings and embodiments, to this
Invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, and does not have to
It is of the invention in limiting.It is worth noting that, in the present invention, hollow ball-shape or hollow ball shape or hollow sphere structure, equal table
What is shown is the physical behavior of tin dioxide material, and expression is the same meaning.
Present example provides a kind of preparation method of phosphatization tin composite material.
Specifically, the preparation method of the phosphatization tin composite material at least includes the following steps:
Tin source material, carbon source material are mixed to and maintain to carry out under alkaline condition hydro-thermal reaction, surface is obtained and is attached with
The hollow stannic oxide ball of carbon source；
Under an inert atmosphere, carbonization treatment is carried out to the hollow stannic oxide ball of acquisition, obtains coated with carbon bed
Hollow stannic oxide ball；
Surface is coated with the hollow stannic oxide ball of carbon-coating and phosphorus source material carries out mixing treatment, and in inert atmosphere
Heating makes the two react, and obtains phosphatization tin composite material；
The phosphatization tin composite material at least contains phosphorization tin, hollow stannic oxide and carbon, and the carbon coating is in the phosphorus
Change the surface of tin, hollow stannic oxide.
Detailed explanation is done to the preparation method of above-mentioned phosphatization tin composite material below.
The tin source material of one of synthesis material as phosphatization tin composite material, can be potassium stannate (K2SnO3·3H2O)、
At least one of sodium stannate.Its both tin source material can be under hydrothermal reaction condition, and generating has the two of hollow ball-shape
Tin oxide.
Carbon source material be used as in the reaction carbon source be attached to generation hollow ball-shape stannic oxide surface, be further carbon
The unsetting carbon for being melted into the stannic oxide surface for being coated on hollow ball-shape establishes carbon source basis.
Preferably, the carbon source material is polyvinyl alcohol.Using polyvinyl alcohol as carbon source material, in hydrothermal reaction process
In, thin layer carbon source is formed on the stannic oxide surface of hollow ball-shape.Through carbonization treatment, become the unsetting carbon coating of indefinite thin layer
Layer.It is further preferred that the concentration of the polyvinyl alcohol during the reaction is 2~10g/L.
Above-mentioned tin source material, carbon source material in mixed process, can using dehydrated alcohol as solvent, can also with go from
Sub- water is as solvent, or using the mixed solution of deionized water and ethyl alcohol as solvent.
Preferably, urea etc. is added in the mixed solution that can be mixed to get to tin source material and carbon source material and is used as soda acid
Regulator, so that the aobvious alkalinity of the pH of mixed solution, in favor of generating the stannic oxide of hollow ball-shape.
The feed ratio of tin source material and carbon source material, can be on the hollow ball-shape stannic oxide surface of formation with carbon source material
Form thin layer clad.I.e. the concentration of carbon source (polyvinyl alcohol) in the reaction is 2~10g/L.
Preferably, the hydrothermal temperature be 120~200 DEG C, the reaction time be 10~for 24 hours, in the hydro-thermal reaction
At a temperature of, obtain the comparatively uniform hollow ball-shape stannic oxide precipitating of partial size.
Hollow ball-shape stannic oxide precipitating obtains to surface after centrifugation, washing, drying and is attached with the hollow ball-shape two of carbon source
Tin oxide.
Above-mentioned when being carbonized to hollow ball-shape stannic oxide, inert atmosphere can be argon gas, helium etc., naturally it is also possible to
It is nitrogen.Preferably, the temperature of carbonization treatment is 350~450 DEG C, and the carbonization treatment time is 4~10h, by carbonization, so that carbon
Source material is completely transformed into unsetting carbon, and is coated on hollow ball-shape stannic oxide surface, forms thin layer clad.
Phosphorus source material of the invention should under heating conditions, generation hydrogen phosphide can be decomposed, by phosphine gas
Reduction reaction occurs with hollow ball-shape stannic oxide and generates metallic tin, and the metallic tin generated further reacts life with hydrogen phosphide
At phosphorization tin (Sn4P3).When phosphorus source quantity of material is enough, then the metallic tin that stannic oxide generates is completely transformed into phosphorization tin,
And a small amount of metallic tin can also be contained if phosphorus source quantity of material is insufficient or heating time is insufficient, in product, at this time
Phosphatization tin composite material in, comprising phosphorization tin, hollow ball-shape stannic oxide, metallic tin and carbon etc..
Preferably, phosphorus source material is sodium hypophosphite (NaH2PO2).Sodium hypophosphite can under lower heating temperature,
It is i.e. decomposable to generate hydrogen phosphide, so that preparation process is more simple.It is further preferred that according to molar ratio, the stannic oxide:
Phosphorus source material=1:1~8.
When Sodium Hypophosphite is as phosphorus source material, preferably heating temperature be 250~300 DEG C, the reaction time be 10min~
2h。
The preparation method of phosphatization tin composite material provided by the present invention passes through water using tin source material combination carbon source material
The hollow stannic oxide ball that surface is attached with carbon source is prepared in thermal response, is then carbonized to carbon source, and with phosphorus source material
Reaction generates hydrogen phosphide, restores hollow stannic oxide by hydrogen phosphide, generates phosphorization tin, and maintain original hollow two
It is swollen that volume can be effectively suppressed when so that the phosphatization tin composite material obtained is as cell negative electrode material in the structural framing of tin oxide
It is swollen, and have good electric conductivity；In addition, this preparation method condition is simple, the requirement to equipment is low, is suitble to large-scale production.
Thus obtained phosphatization tin composite material, according to mass percentage meter, the phosphatization tin composite material contains 5~
98% phosphorization tin, 2~90% hollow stannic oxide.In addition, the phosphorus content in phosphatization tin composite material, coats for thin layer
Amount, is usually no more than the 15% of phosphatization tin composite material gross mass.Further, the phosphatization tin composite material that the present invention obtains
In, a small amount of metallic tin can also be contained.
Hollow ball shape structure is conducive to slow down phosphatization tin composite material as lithium ion battery or sodium-ion battery cathode
The material disintegrating bring capacitance loss in charge and discharge process, to extend the cycle life of battery, and phosphorization tin then has and mentions
The effect of high material coulombic efficiency for the first time.
Exactly because in this way, the present invention furthermore provides a kind of anode plate for lithium ionic cell or sodium-ion battery cathode
Piece, the anode plate for lithium ionic cell or sodium-ion battery negative electrode tab contain negative electrode active material, and the negative electrode active material is
The phosphatization tin composite material that the preparation method of phosphatization tin composite material of the present invention is prepared.Specifically, lithium ion battery is negative
The negative electrode active material of pole piece or the negative electrode active material of sodium-ion battery negative electrode tab at least contain phosphorization tin, hollow titanium dioxide
Tin and carbon, the carbon coating is in the surface of phosphorization tin, hollow stannic oxide.
Preferably, the phosphatization tin composite material contains 5~98% phosphorization tin, 2~90% hollow stannic oxide, carbon
Content is 1~15%.
In addition, the negative electrode active material can also contain a small amount of metallic tin.
So far, the present invention furthermore provides a kind of lithium ion battery or sodium-ion battery, either lithium ion battery
Or sodium-ion battery includes negative electrode tab, and the negative electrode tab contains phosphatization tin composite material, and the phosphatization tin composite material is extremely
Contain phosphorization tin, hollow stannic oxide and carbon less, the carbon coating is in the surface of phosphorization tin, hollow stannic oxide.
Preferably, the phosphatization tin composite material in the lithium ion battery or sodium-ion battery negative electrode tab contains 5
~98% phosphorization tin, 2~90% hollow stannic oxide, carbon content are 1~15%.
More effectively to illustrate technical solution of the present invention, below by multiple specific embodiment explanations.
Embodiment 1
A kind of preparation method of phosphatization tin composite material, specifically includes the following steps:
(1) K of 1.5g is weighed2SnO3·3H2O (potassium stannate), 1.2g urea, 1.2g polyvinyl alcohol (alcoholysis degree 87%),
Prepare deionized water 180mL, dehydrated alcohol 120mL simultaneously；
(2) by above-mentioned potassium stannate, polyvinyl alcohol, urea, deionized water, dehydrated alcohol mix to uniformly after, obtain first
First mixed material is then placed in the reaction kettle of polytetrafluoroethylliner liner by mixed material, at 150 DEG C, reaction
15h is centrifuged and is cleaned with ethyl alcohol and deionized water, is dried in vacuo 12h at 60 DEG C.
(3) dried sample is placed in tube furnace, is passed through argon gas, 4h is reacted at 400 DEG C, obtains surface after cooling
It is coated with the hollow ball-shape tin dioxide material of unsetting carbon.
(4) the hollow ball-shape tin dioxide material for taking 1.5g step (3) to obtain is mixed with the sodium hypophosphite of 5g, is mixed
It is placed in tube furnace, is passed through argon gas, be heated to 280 DEG C, keep the temperature 10min, subsequent natural cooling through deionized water cleaning, is done
Composite material is obtained after dry.
Corresponding performance detection is carried out to the composite material that embodiment 1 obtains, including scanning electron microscope (SEM) test, XRD are surveyed
Battery is tried and is assembled into be tested.
Wherein, SEM scanning is as shown in Figure 1, from fig. 1, it can be seen that the composite material overwhelming majority is spherical in shape, and is hollow shape,
Spherical composite material surface is coated with a small amount of other compositions, and without apparent agglomeration between particle；
Fig. 2 is the XRD diagram of 1 composite material of embodiment, and as can be seen from Figure 2, obtained composite material contains phosphorization tin, tin and two
Tin oxide.
Thus the composite material that can determine is phosphatization tin composite material, takes determining phosphatization tin composite material 0.14g,
Conductive carbon microballoon 0.02g, sodium carboxymethylcellulose 0.4g (solid content 5wt%), after mixing, coated in 7 μm of copper foil
On, dried pole piece is cut into the former piece of 12mm by 80 DEG C of dryings in vacuum drying oven, drying time 12h, is lithium metal to electrode
Piece is assembled into button cell, and the solvent of the electrolyte of the button cell is ethylene carbonate: diethyl carbonate: fluoro carbonic acid second
Enester=1:1:0.05 (volume ratio), solute are lithium hexafluoro phosphate, and the concentration of lithium hexafluoro phosphate is 1mol/L.It is followed after standing
The test of ring voltammetry, ac impedance measurement, the cyclic curve test of different multiplying and 400mA/g current density, at room temperature
Cyclic curve, wherein Fig. 3 be cyclic voltammetry curve, Fig. 4 be AC impedance curve, Fig. 5 be different multiplying cyclic curve, figure
6 be cyclic curve of the button cell at room temperature with current density for 400mA/g.
As can be seen from Figure 3, the current potential of material Li insertion extraction ion under the conditions of charge and discharge is stablized；
As can be seen from Figure 4, the impedance of battery pole piece is smaller；
As can be seen from Figure 5, illustrate that material has good high rate performance；
As can be seen from Figure 6, illustrate that material has good cycle performance.
Embodiment 2
A kind of preparation method of phosphatization tin composite material, specifically includes the following steps:
(1) K of 1.5g is weighed2SnO3·3H2O (potassium stannate), 1.2g urea, 1.2g polyvinyl alcohol (alcoholysis degree 87%),
Prepare deionized water 300mL simultaneously；
(2) by above-mentioned potassium stannate, polyvinyl alcohol, urea, deionized water mix to uniformly after, obtain the first mixed material,
Then first mixed material is placed in the reaction kettle of polytetrafluoroethylliner liner, at 150 DEG C, reacts 15h, centrifugation is used in combination
Ethyl alcohol and deionized water cleaning, are dried in vacuo 12h at 60 DEG C.
(3) dried sample is placed in tube furnace, is passed through argon gas, 4h is reacted at 400 DEG C, obtains surface after cooling
It is coated with the hollow ball-shape tin dioxide material of unsetting carbon.
(4) the hollow ball-shape tin dioxide material for taking 1.5g step (3) to obtain is mixed with the sodium hypophosphite of 8g, is mixed
It is placed in tube furnace, is passed through argon gas, be heated to 280 DEG C, keep the temperature 15min, subsequent natural cooling through deionized water cleaning, is done
Composite material is obtained after dry.
Corresponding performance detection is carried out to the composite material that embodiment 2 obtains, including scanning electron microscope (SEM) test, XRD are surveyed
Battery is tried and is assembled into be tested.
Wherein, Fig. 7 is XRD test, and as can be seen from Figure 7, composite material contains phosphorization tin and stannic oxide.
Fig. 8 is SEM scanning, as it can be observed in the picture that the composite material overwhelming majority is spherical in shape, and is hollow shape, spherical composite wood
Material surface is coated with a small amount of other compositions, and without apparent agglomeration between particle.
Fig. 9 be Fig. 8 box in element EDS map, as can be seen from Figure 9, in the region in contain Sn, P, C and O, the result and
The XRD test result of Fig. 7 is with uniformity, illustrates that the composite material that the present embodiment 2 obtains is phosphatization tin composite material really.
Thus the composite material that can determine is phosphatization tin composite material, takes determining phosphatization tin composite material 0.14g,
Conductive carbon microballoon 0.02g, PVDF0.4g (solid content 5wt%), after mixing, coated on 7 μm of copper foils, vacuum drying oven
In 80 DEG C of dryings, dried pole piece is cut into the former piece of 12mm by drying time 12h, is metal lithium sheet to electrode, is assembled into knob
Battery is detained, the solvent of the electrolyte of the button cell is ethylene carbonate: diethyl carbonate: fluorinated ethylene carbonate=1:1:
0.05 (volume ratio), solute are lithium hexafluoro phosphate, and the concentration of lithium hexafluoro phosphate is 1mol/L.Corresponding performance survey is carried out after standing
Examination, wherein Figure 10 is room temperature cycles curve of the button cell under 400mA/g current density, and Figure 11 is the high rate performance of battery.
As can be seen from Figure 10, battery still has good cycle performance under the current density of 400mA/g；
As can be seen from Figure 11, battery all has higher capacity under different current densities.
From the result of embodiment 1 and embodiment 2 it is found that the preparation method of phosphatization tin composite material of the present invention, is prepared
Phosphatization tin composite material contain phosphorization tin and stannic oxide really, and stannic oxide is hollow ball-shape structure, phosphorization tin and
Stannic oxide surface is coated with carbon-coating, and the phosphatization tin composite material of this composition is as lithium ion battery, charge-discharge cycle
Can be good, mainly have benefited from the stannic oxide of hollow ball-shape structure, is able to maintain the stability of material structure in charge and discharge process,
Inhibit expansion, surface coated carbon-coating is conducive to improve the conductivity of material, therefore is suitble to promote and apply.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc. within mind and principle should all include within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of phosphatization tin composite material, which is characterized in that at least include the following steps:
Tin source material, carbon source material are mixed to and maintain to carry out under alkaline condition hydro-thermal reaction, surface is obtained and is attached with carbon source
Hollow stannic oxide ball；
Under an inert atmosphere, carbonization treatment is carried out to the hollow stannic oxide ball of acquisition, obtains the sky of coated with carbon bed
Heart stannic oxide ball；
Surface is coated with the hollow stannic oxide ball of carbon-coating and phosphorus source material carries out mixing treatment, and is heated in inert atmosphere
So that the two is reacted, obtains phosphatization tin composite material；
The phosphatization tin composite material at least contains phosphorization tin, hollow stannic oxide and carbon, the carbon coating in the phosphorization tin,
The surface of hollow stannic oxide.
2. the preparation method of phosphatization tin composite material as described in claim 1, which is characterized in that the tin source material is stannic acid
At least one of potassium, sodium stannate；
And/or the carbon source material is polyvinyl alcohol；
And/or phosphorus source material is sodium hypophosphite.
3. the preparation method of phosphatization tin composite material as described in claim 1, which is characterized in that the hydrothermal temperature is
120~200 DEG C, the reaction time be 10~for 24 hours.
4. the preparation method of phosphatization tin composite material as described in claim 1, which is characterized in that the temperature of the heating reaction
It is 250~300 DEG C, the reaction time is 10min~2h.
5. the preparation method of phosphatization tin composite material as claimed in claim 1 or 2, which is characterized in that carbon source described in reaction
Poly- concentration be 2~10g/L.
6. the preparation method of phosphatization tin composite material as described in claim 1, which is characterized in that according to molar ratio, described two
Tin oxide: phosphorus source material=1:1~8.
7. a kind of phosphatization tin composite material, which is characterized in that the phosphatization tin composite material at least contains phosphorization tin, hollow dioxy
Change tin and carbon, the carbon coating is in the surface of phosphorization tin, hollow stannic oxide.
8. phosphatization tin composite material as claimed in claim 7, which is characterized in that according to mass percentage meter, the phosphatization
Tin composite material contains 5~98% phosphorization tin, 2~90% hollow stannic oxide.
9. a kind of lithium ion battery or sodium-ion battery negative electrode tab, including negative electrode active material, which is characterized in that the cathode is living
Property material be phosphatization tin composite material, the phosphatization tin composite material at least contains phosphorization tin, hollow stannic oxide and carbon, described
Carbon coating is in the surface of phosphorization tin, hollow stannic oxide.
10. a kind of lithium ion battery or sodium-ion battery, including negative electrode tab, which is characterized in that the negative electrode tab contains phosphorization tin
Composite material, the phosphatization tin composite material at least contain phosphorization tin, hollow stannic oxide and carbon, and the carbon coating is in phosphatization
The surface of tin, hollow stannic oxide.
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