CN109921000A - The anode material for lithium-ion batteries and preparation method thereof of surface cladding piezoelectric material - Google Patents
The anode material for lithium-ion batteries and preparation method thereof of surface cladding piezoelectric material Download PDFInfo
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- CN109921000A CN109921000A CN201910222253.6A CN201910222253A CN109921000A CN 109921000 A CN109921000 A CN 109921000A CN 201910222253 A CN201910222253 A CN 201910222253A CN 109921000 A CN109921000 A CN 109921000A
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- lithium
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- 239000000463 material Substances 0.000 title claims abstract description 150
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 80
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000005253 cladding Methods 0.000 title claims abstract description 43
- 239000010405 anode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 12
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 10
- WSMQKESQZFQMFW-UHFFFAOYSA-N 5-methyl-pyrazole-3-carboxylic acid Chemical compound CC1=CC(C(O)=O)=NN1 WSMQKESQZFQMFW-UHFFFAOYSA-N 0.000 claims abstract description 9
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 claims abstract description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 3
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims abstract description 3
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims abstract description 3
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- 229910052744 lithium Inorganic materials 0.000 claims description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 34
- 238000001704 evaporation Methods 0.000 claims description 21
- 230000008020 evaporation Effects 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 239000006183 anode active material Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000008240 homogeneous mixture Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000010450 olivine Substances 0.000 claims description 3
- 229910052609 olivine Inorganic materials 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910006703 Li—Ni—Mn—O Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 13
- 230000005518 electrochemistry Effects 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- 238000009792 diffusion process Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 239000013590 bulk material Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 25
- 238000001354 calcination Methods 0.000 description 14
- 239000010406 cathode material Substances 0.000 description 14
- 238000000227 grinding Methods 0.000 description 14
- 238000010792 warming Methods 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 8
- 229910012463 LiTaO3 Inorganic materials 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 229910032387 LiCoO2 Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 5
- 229910003327 LiNbO3 Inorganic materials 0.000 description 4
- 239000002305 electric material Substances 0.000 description 4
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 229910008537 Li1.2Mn0.56Ni0.17Co0.07O2 Inorganic materials 0.000 description 3
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- 229910009740 Li2GeO3 Inorganic materials 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910003378 NaNbO3 Inorganic materials 0.000 description 2
- 229910003256 NaTaO3 Inorganic materials 0.000 description 2
- 229910003781 PbTiO3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910010252 TiO3 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- -1 diaphragm Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002319 LaF3 Inorganic materials 0.000 description 1
- 229910001477 LaPO4 Inorganic materials 0.000 description 1
- 229910007626 Li2SnO3 Inorganic materials 0.000 description 1
- 229910007822 Li2ZrO3 Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910015944 LiMn0.8Fe0.2PO4 Inorganic materials 0.000 description 1
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014063 LiNi1-xCoxO2 Inorganic materials 0.000 description 1
- 229910014094 LiNi1-xMnxO2 Inorganic materials 0.000 description 1
- 229910014402 LiNi1—xCoxO2 Inorganic materials 0.000 description 1
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014891 LiNi1−xMnxO2 Inorganic materials 0.000 description 1
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910012305 LiPON Inorganic materials 0.000 description 1
- 229910012985 LiVO3 Inorganic materials 0.000 description 1
- 229910015278 MoF3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N bismuth(III) nitrate Inorganic materials [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- FASQHUUAEIASQS-UHFFFAOYSA-K molybdenum trifluoride Chemical compound F[Mo](F)F FASQHUUAEIASQS-UHFFFAOYSA-K 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical compound F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of anode material for lithium-ion batteries and preparation method thereof of surface cladding piezoelectric material, cell positive material surface has coated one layer of piezoelectric material with piezoelectric effect；The piezoelectric material includes that the barium titanate with piezoelectric property, lithium niobate, sodium niobate, lithium tantalate, inclined potassium-sodium niobate and inclined strontium barium niobate are any one or more of.The piezoelectric property that the present invention efficiently uses piezoelectric material realizes the effect of coating modification to positive electrode active materials, guarantee that the bulk structure of positive electrode active materials is unaffected and destroys, inhibit the growth of solid-electrolyte interface film, improve active material-cladding bed boundary lithium ion diffusion velocity, to effectively improve the structural stability and electrochemistry cycle performance of anode material for lithium-ion batteries, the pyrolysis temperature for improving positive bulk material, to promote the security performance in lithium ion battery use process.
Description
Technical field
The present invention relates to the field of surface modification of new energy anode active material of lithium ion battery, and in particular to a kind of surface
Coat the anode material for lithium-ion batteries and preparation method thereof of piezoelectric material.
Background technique
Lithium ion battery is to be taken the lead in realizing commercialization in nineteen ninety by Japanese Sony company, because of its, storage high with specific energy
The advantages such as energy efficiency height are gradually applied to the energy such as energy-storage system, mobile electronic device, electric vehicle neck in recent years
Domain.Lithium ion battery main composition material includes electrolyte, diaphragm, positive electrode and negative electrode material, and wherein positive electrode occupies
It is the critical material for pushing performance of lithium ion battery to be promoted, therefore prepare the lithium ion pond with good physical and chemical performance just than big
Pole material improves the physical and chemical performance of existing lithium ion cell positive bulk material particularly important.
Currently, anode material for lithium-ion batteries mainly has layer structure cobalt acid lithium (LiCoO2, LCO), lithium nickelate (LiNiO2,
) and derivative LNO；Spinel structure LiMn2O4 (LiMn2O4, LMO) and derivative；Olivine structure lithium iron phosphate (LiFePO4,
LFP), iron manganese phosphate for lithium (LiMn0.8Fe0.2PO4, LMFP) and derivative；Ternary layered material, rich lithium ternary material and derivative
Deng.Wherein, LCO material is current compacted density highest, specific energy highest while being also to realize commercialized positive material earliest
Material, but cobalt resource is limited, at high cost, and when de- lithium amount is more than 55 %, the structural stability of material declines rapidly, the service life and
Safety is deteriorated rapidly.Though LNO material is resourceful, cheap, there is higher capacity, there is preparation difficulty, material knot
The problems such as structure is unstable, cycle performance of battery is poor.LMO and LFP material feedstock is abundant, at low cost, but its specific energy is low, simultaneously
LMO material haves the shortcomings that cyclical stability is poor.Stratiform ternary material there is also resources costs, sintering atmosphere cost, prepare item
The problems such as part is harsh, battery preparation condition and technical threshold is high.Therefore, for or being expected to obtain industry application at present
Promotion of the anode material for lithium-ion batteries in indexs such as structural stability, cycle efficieny, high rate performance, security performances, Ke Yigeng
Meet lithium ion battery industry well to positive electrode requirements, to effectively push the application of lithium-ion-power cell.
With deep and material preparation technology the development of material physical chemistry research, it has been found that high-performance lithium ion electricity
The preparation of pond positive electrode can be from the cell configuration of bulk material, primary particle crystal structure, second particle structure, material table
Chemistry four aspects in face are set about.Wherein, material surface chemistry refers mainly to the gradient distribution etc. of surface cladding and surface-element concentration, excellent
The performance of material can significantly be promoted by changing material surface and interface physico-chemical property.It is numerous studies have shown that using surface cladding can have
Effect promotes positive electrode surface micro-structure stability and surface and interface lithium ion kinetics of diffusion behavior, to positive electrode active materials structure
It plays an important role with electrochemical stability.
In recent years, oxide (Al2O3, MgO, ZrO2, ZnO, SiO2, SnO2, La2O3), fluoride (AlF3, MoF3, LaF3,
ZrF3), phosphate (AlPO4, YPO4, LaPO4, Li3PO4), fast-ionic conductor (LiVO3, LiPON, Li2ZrO3, Li2SnO3) etc. materials
Material is widely used in positive electrode LiCoO2, LiNi1-xCoxO2, LiNi1-xMnxO2, LiNi1-x-yCoxMnyO2,
LiNi0.5Mn1.5O4, xLi2MnO3·(1-x)LiMO2The surface modification of (0 < x < 1,0 < y < 1, x+y=1, M=Mn, Ni, Co) changes
Property.Correlative study the result shows that, they can pass through barrier positive electrode active materials and electrolyte in positive electrode surface cladding
It directly contacts, effectively inhibits the growth of SEI film and the structure degradation of surface and interface, to improve the stability and heat of electrode material
Safety.However, positive electrode active materials in electrochemistry cyclic process there are lasting bulk structure phase transformation, lead to material structure
Stability declines and the ion diffusion of positive electrode active materials and cladding bed boundary is relatively slow and material thermal safety problem is still
Restraining factors urgently to be resolved.
It exists in the prior art and piezoceramic material is added into positive electrode active materials presoma, i.e., by positive electrode active materials
Mixed with piezoceramic material, make piezoceramic material enhance in positive electrode ion diffusion, but and not formed clad,
For the material because destroying the bulk structure of positive electrode active materials, stability is poor.It has been prepared in addition, also having in positive electrode structure
Piezoelectric material covering is carried out in entire positive electrode surface after, which changed using the piezoelectric properties of piezoelectric material coating
Electrical transport in entire battery.
The present invention is proposed to positive electrode active materials obtained using sol-gal process progress piezoelectric material surface cladding, no
It can only guarantee that the bulk structure of positive electrode active materials is unaffected and destroys, and the piezoelectricity of piezoelectric material can be efficiently used
Characteristic realizes the effect of coating modification to positive electrode active materials, i.e., enhances on the basis of the bulk structure of not broken positive electrode active materials
Ion solves clad in the prior art and ion is inhibited to ask in the technology of cladding interface electronic transport in the diffusion at cladding interface
Topic.
Summary of the invention
Modified to anode active material of lithium ion battery existing insufficient for existing surface covering material, the present invention proposes
A kind of method that piezoelectric material is used for Li-ion batteries, i.e., it is living as anode using piezoelectric material
The surface covering material of property material.By uniform piezoelectric material cladding not only can to avoid lithium ion pond positive electrode active materials with
The direct contact of electrolyte, improves the surface stability of electrode material, to be conducive to improve the cyclical stability of positive electrode.
Importantly, crystal microstructure changes bring stress variation in electrochemistry cyclic process using positive electrode active materials, make
Surface coated piezoelectric material generates piezoelectricity gesture, to effectively improve interface ion diffusivity and further increase the dynamic of battery
Mechanical property.In addition, uniform piezoelectric material clad has specific Curie temperature, can effectively improve to varying degrees
The thermal safety of positive electrode active materials reduces security risk.
Realize the technical scheme is that
A kind of anode material for lithium-ion batteries of surface cladding piezoelectric material, cell positive material surface, which has coated one layer, has pressure
The piezoelectric material of electrical effect.
The piezoelectric material includes with barium titanate, lithium niobate, sodium niobate, lithium tantalate, inclined niobic acid with piezoelectric property
Potassium sodium and inclined strontium barium niobate are any one or more of.
The cell positive material is cobalt acid lithium, lithium nickelate and the derivative of layer structure；Ternary layered material, Fu Li tri-
First material and derivative；Spinel structure Li-Ni-Mn-O, LiMn2O4 and derivative；Olivine structure lithium iron phosphate and derivative.
The piezoelectric material accounts for the 0.1-5 wt. % of cell positive material quality.
The preparation method of the anode material for lithium-ion batteries of the surface cladding piezoelectric material, steps are as follows:
(1) piezoelectric material presoma is dissolved in the acid solution with chelation, is obtained through strong stirring finely dispersed
Piezoelectric material precursor mixed solution；
(2) in a solvent by anode active material of lithium ion battery dispersion, agitated to obtain evenly dispersed dispersion liquid；Solvent is
Ultrapure water, deionized water, alcohol solvent are any one or more of；
(3) piezoelectric material precursor mixed solution obtained in step (1) is mixed with dispersion liquid obtained in step (2), is passed through
Strong stirring obtains homogeneous mixture solotion；
(4) the homogeneous mixture solotion evaporation ageing obtained step (3), using stirring evaporation or water-bath evaporation or oil bath evaporation side
Any one of formula obtains anode active material of lithium ion battery and piezoelectric material presoma complex sol, complex sol is existed
It is sufficiently dry in air blast or vacuum oven, form xerogel；
(5) xerogel obtained by step (4) is fully ground, obtained after annealed processing the lithium of coated with uniform piezoelectric material from
Sub- cell positive material.
Piezoelectric material presoma is in nitrate, acetate, ethylate or the oxide of piezoelectric material in the step (1)
Any one；Acid solution is the ethanol solution of citric acid or tartaric acid, keep piezoelectric material presoma fully dispersed, makes to mix
The concentration for closing solution is 1.0g/L-2.0g/L.
The mass ratio of piezoelectric material presoma and anode active material of lithium ion battery in step (2) in the step (1)
For (0.001-0.05): 1.
The temperature of evaporation ageing is 60-120 DEG C in the step (4), until obtaining its gel；Drying temperature is 80-120
DEG C, time 10-12h.
Annealing temperature is 500-900 DEG C in the step (5), annealing time 6-48h.
The beneficial effects of the present invention are:
(1) piezoelectric material is evenly coated at anode active material of lithium ion battery surface, easily operated, repeated strong, is conducive to
Commercial applications.It is proposed by the present invention that piezoelectric material is evenly coated at surface of positive electrode active material is as shown in Figure 1.
(2) as shown in Fig. 2, the piezoelectric material uniformly coated can be used as protective layer isolation positive electrode active materials and electrolyte
Direct contact, thus effectively inhibit side reaction and solid-electrolyte interface film growth.
(3) as shown in figure 3, efficiently using positive electrode active materials in electrochemistry cyclic process due to material by piezoelectric effect
Expect phase transformation bring stress variation, improve active material-cladding bed boundary lithium ion diffusion velocity, thus effectively improve lithium from
The structural stability and electrochemistry cycle performance of sub- cell positive material.
It (4), can be to varying degrees as shown in figure 4, uniform piezoelectric material clad has specific Curie temperature
The thermal safety of positive electrode active materials is effectively improved, security risk is reduced.
To sum up, the present invention has pressure in anode active material of lithium ion battery coated with uniform using sol-gel method
On the one hand the piezoelectric material of electrical characteristics has obstructed directly contacting, inhibiting solid-electrolyte for positive electrode active materials and electrolyte
The growth of interfacial film；On the other hand positive electrode active materials are efficiently used in electrochemistry cyclic process due to material by piezoelectric effect
Expect phase transformation bring stress variation, improve active material-cladding bed boundary lithium ion diffusion velocity, thus effectively improve lithium from
The structural stability and electrochemistry cycle performance of sub- cell positive material, as shown in Figure 5.
A is the schematic diagram with the anode material for lithium-ion batteries full-package structure of piezoelectric effect in Fig. 5, inside be by
The positive electrode of modification, outside package ribbon grain are the color range figures of voltage, with the potential of quantitative description clad generation
Size；B represents the state before charging, positive electrode, and the bead of the inside represents lithium ion, and lower layer indicates piezoelectricity clad, upper layer
For positive electrode material layer；C represents the state in charging process, and when charging starts, lithium ion passes through piezoelectricity clad from positive electrode
Abjection outward, positive electrode expand (top section broadens), generate extruding to piezoelectricity clad (underclad portion), produce in clad
Raw piezoelectricity gesture (arrow in lower layer), the direction of piezoelectricity gesture is upward, contrary with the dispersal direction of lithium ion and applied voltage；
D represents the state that charging terminates, and at the end of charging, the lithium ion in positive electrode is all deviate from, and positive electrode expansion is most aobvious
(top section is maximum) is write, at this time piezoelectricity clad (underclad portion) maximum subject to downward force, corresponding to clad at this time
Internal piezoelectricity gesture is maximum, and pressure electric potential direction at this time is opposite with lithium ion dispersal direction and direction of an electric field；E represents electric discharge shape
State, electric discharge start, and lithium ion begins through piezoelectricity clad (underclad portion) and is embedded in (top section) to positive electrode, positive material
The expansion of material gradually reduces (underclad portion is smaller and smaller), and the pressure of piezoelectricity clad is reduced, internal piezoelectricity gesture is corresponded to
Reduce, but direction is still upward, it is consistent with the dispersal direction of lithium ion and extra electric field direction；The electric discharge of F table is completed, electric discharge knot
Shu Shi, most of lithium ion return to positive (having most bead in top section), still have part that can not return, and correspond to just
Pole material can not return to home position, still have compared with most starting some expansions (top section that top section is slightly larger than B), still
So there is pressure to clad (underclad portion), minimum corresponding to piezoelectricity gesture at this time, direction is with lithium ion dispersal direction and outside
It is consistent to be powered on field direction.
In addition, the uniform piezoelectric material clad has specific Curie temperature, can effectively improve to varying degrees
The thermal safety of positive electrode active materials reduces security risk.Compared to the cladding material having to anode active material of lithium ion battery
Material, in the present invention piezoelectric material that proposes uniformly coat can be improved positive electrode active materials body phase and interface structural stability,
And chemical property and the thermally safe characteristic of battery.
A kind of anode material for lithium-ion batteries full-package structure and preparation side with piezoelectric effect provided by the invention
Method obtains modified anode active material of lithium ion battery by simple and easy preparation process, can not only guarantee anode
The bulk structure of active material is unaffected and destroys, and can efficiently use the piezoelectric property of piezoelectric material to positive-active
The effect of material realization coating modification: directly contacting, inhibiting solid-for positive electrode active materials and electrolyte has on the one hand been obstructed
The growth of electrolyte interface film；On the other hand positive electrode active materials are efficiently used in electrochemistry cyclic process by piezoelectric effect
Due to material phase transformation bring stress variation, active material-cladding bed boundary lithium ion diffusion velocity is improved, to effectively mention
The structural stability and electrochemistry cycle performance of high-lithium ion cell positive material.In addition, selection coated with uniform have compared with
The piezoelectric material of low Curie temperature, can effectively improve the pyrolysis temperature of positive bulk material, so that promoting lithium ion battery makes
With security performance in the process.In conclusion proposed by the invention uses piezoelectric material to anode material for lithium-ion batteries packet
Modified strategy is covered, can effectively improve structural stability, lithium ion diffusion coefficient, thermal safety of positive bulk material etc.,
To obtain the anode active material of lithium ion battery having compared with high circulation stability, high rate performance and thermal safety.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is before 1 lithium ion battery lithium-rich anode surface of active material of the embodiment of the present invention coats piezoelectric material lithium tantalate
Scanning electron microscope and transmission electron microscope image afterwards.As the result is shown, it can be seen that lithium tantalate clad equably wraps
Overlay on lithium-rich anode surface of active material.
Fig. 2 is before 1 lithium ion battery lithium-rich anode surface of active material of the embodiment of the present invention coats piezoelectric material lithium tantalate
Afterwards, the electrode infrared test data before and after electrochemistry circulation.The results show that piezoelectric material clad structure effectively inhibits admittedly
The growth of body-electrolyte interface film.
Fig. 3 is before 1 lithium ion battery lithium-rich anode surface of active material of the embodiment of the present invention coats piezoelectric material lithium tantalate
Circulation and high rate performance afterwards.The results show that the structure that piezoelectric material clad structure effectively increases positive electrode active materials is steady
Qualitative and Li-ion kinetics behavior.
Fig. 4 is before 1 lithium ion battery lithium-rich anode surface of active material of the embodiment of the present invention coats piezoelectric material lithium tantalate
Heat analysis test data afterwards.As the result is shown, it can be seen that the lithium-rich anode active material tantalum with piezoelectric material clad structure
Its thermal stability of sour lithium is significantly improved.
Fig. 5 is that 1 lithium ion battery lithium-rich anode active material lithium tantalate particle surface of the embodiment of the present invention has piezoresistive material
The mechanism of action after material clad structure in electrochemistry cyclic process details the generation of the piezoelectricity gesture of piezoelectric material and improves lithium
Ion is in positive electrode-cladding bed boundary transmission dynamic behavior.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
Piezoelectric material LiTaO3Coated lithium ion battery lithium-rich anode material Li1.2Mn0.56Ni0.17Co0.07O2。
(1) Ta of 0.1 M is configured2O5、C4H6O6And CH3COOLi is dissolved in ethanol solution, is proportionally chosen, by it
It instills in the positive electrode solution being dissolved in ethyl alcohol, 8 h is then mixed；
(2) above-mentioned mixed solution is warming up to 100 °C, stirring evaporation obtains then in 120 °C of dry 12 h of drying box
Xerogel；
(3) it will be put into crucible after the grinding of above-mentioned xerogel, 500 °C of 48 h of calcining, cooled to room temperature obtains piezoelectricity
Material LiTaO3The lithium-rich anode material of cladding.
Embodiment 2
Piezoelectric material BaTiO3Coated lithium ion battery lithium-rich anode material Li1.2Mn0.56Ni0.17Co0.07O2。
(1) Ba of 0.1 M is configured2CO3、C6H8O7And C16H36CO4Ti is dissolved in ethanol solution, is proportionally chosen, will
It is instilled in the positive electrode solution being dissolved in ethyl alcohol, and 10 h are then mixed；
(2) above-mentioned mixed solution is warming up to 80 °C, stirring evaporation is done then in 80 °C of dry 12 h of drying box
Gel；
(3) it will be put into crucible after the grinding of above-mentioned xerogel, 900 °C of 12 h of calcining, then cooled to room temperature, obtains
Piezoelectric material BaTiO3The lithium-rich anode material of cladding.
Embodiment 3
Piezoelectric material LiNbO3Coated lithium ion battery lithium iron phosphate positive material LiFePO4。
(1) Nb of 0.1 M is configured2O5、C4H6O6And CH3COOLi is dissolved in ethanol solution, is proportionally chosen, by it
It instills in the positive electrode solution being dissolved in ethyl alcohol, 8 h is then mixed；
(2) above-mentioned mixed solution is warming up to 120 °C, stirring evaporation obtains then in 120 °C of dry 12 h of drying box
Xerogel；
(3) it will be put into crucible after the grinding of above-mentioned xerogel, 550 °C of 24 h of calcining, cooled to room temperature obtains piezoelectricity
Material LiNbO3The lithium iron phosphate positive material of cladding.
Embodiment 4
Piezoelectric material NaNbO3Coated lithium ion battery manganate cathode material for lithium LiMn2O4。
(1) Nb of 0.1 M is configured2O5、C4H6O6And NaNO3It is dissolved in ethanol solution, proportionally chooses, instilled
It is dissolved in the positive electrode solution in ethyl alcohol, 10 h is then mixed；
(2) above-mentioned mixed solution is warming up to 120 °C, stirring evaporation obtains then in 120 °C of dry 12 h of drying box
Xerogel；
(3) it will be put into crucible after the grinding of above-mentioned xerogel, 550 °C of 24 h of calcining, cooled to room temperature obtains piezoelectricity
Material NaNbO3The manganate cathode material for lithium of cladding.
Embodiment 5
Piezoelectric material NaTaO3Coated lithium ion battery nickel lithium manganate cathode material LiNi0.5Mn1.5O4。
(1) Ta of 0.1 M is configured2O5、C4H6O6And NaNO3It is dissolved in ethanol solution, proportionally chooses, instilled
It is dissolved in the positive electrode solution in ethyl alcohol, 12 h is then mixed；
(2) above-mentioned mixed solution is warming up to 100 °C, stirring evaporation obtains then in 120 °C of dry 10 h of drying box
Xerogel；
(3) it will be put into crucible after the grinding of above-mentioned xerogel, 500 °C of 48 h of calcining, cooled to room temperature obtains piezoelectricity
Material NaTaO3The nickel lithium manganate cathode material of cladding.
Embodiment 6
Piezoelectric material LiGaO3Coated lithium ion battery nickel lithium manganate cathode material LiNi0.5Mn1.5O4。
(1) Li of 0.1 M is configured2CO3、C6H8O7And Ga2O3It is dissolved in ultra-pure water solution, proportionally chooses, by it
It instills in the positive electrode solution being dissolved in ultrapure water, 10 h is then mixed；
(2) above-mentioned mixed solution is warming up to 100 °C, stirring evaporation obtains then in 100 °C of dry 12 h of drying box
Xerogel；
(3) it will be put into crucible after the grinding of above-mentioned xerogel, 900 °C of 12 h of calcining, then cooled to room temperature, obtains
Piezoelectric material LiGaO3The nickel lithium manganate cathode material of cladding.
Embodiment 7
Piezoelectric material Bi0.5Na0.5TiO3Coated lithium ion battery lithium cobaltate cathode material LiCoO2。
(1) NaNO of 0.1 M is configured3、C6H8O7、Bi(NO3)3And C16H36CO4Ti is dissolved in acetic acid solution, proportionally
It chooses, is instilled in the positive electrode solution being dissolved in acetic acid, 8 h are then mixed；
(2) above-mentioned mixed solution is warming up to 60 °C, stirring evaporation obtains dry solidifying then in 90 °C of dry 10 h of drying box
Glue；
(3) it will be put into crucible after the grinding of above-mentioned xerogel, 900 °C of 12 h of calcining, then cooled to room temperature, obtains
Piezoelectric material Bi0.5Na0.5TiO3The lithium cobaltate cathode material of cladding.
Embodiment 8
Piezoelectric material BaZr0.1Ti0.9O3Coated lithium ion battery lithium cobaltate cathode material LiCoO2。
(1) Ba of 0.1 M is configured2CO3、C6H8O7And C16H36CO4Ti is dissolved in ethanol solution, is proportionally chosen, will
It is instilled in the positive electrode solution being dissolved in ethyl alcohol, and 10 h are then mixed；
(2) above-mentioned mixed solution is warming up to 80 °C, stirring evaporation is done then in 80 °C of dry 12 h of drying box
Gel；
(3) it will be put into crucible after the grinding of above-mentioned xerogel, 750 °C of 6 h of calcining, then cooled to room temperature, is pressed
Electric material BaZr0.1Ti0.9O3The lithium cobaltate cathode material of cladding.
Embodiment 9
Piezoelectric material PbTiO3The nickelic positive electrode LiMn of coated lithium ion battery0.1Ni0.8Co0.1O2。
(1) Pb (CH of 0.1 M is configured3COO)2、C6H8O7And C16H36CO4Ti is dissolved in ethanol solution, is proportionally selected
It takes, is instilled in the positive electrode solution being dissolved in ethyl alcohol, 6 h are then mixed；
(2) above-mentioned mixed solution is warming up to 60 °C, stirring evaporation is done then in 80 °C of dry 10 h of drying box
Gel；
(3) it will be put into crucible after the grinding of above-mentioned xerogel, 700 °C of 8 h of calcining, then cooled to room temperature, is pressed
Electric material PbTiO3The nickelic positive electrode of cladding.
Embodiment 10
Piezoelectric material Li2GeO3The nickelic positive electrode LiMn of coated lithium ion battery0.1Ni0.8Co0.1O2。
(1) GeO of 0.1 M is configured2And LiOH is dissolved in ultrapure water, is proportionally chosen, instilled be dissolved in it is ultrapure
In the positive electrode solution of water, 6 h are then mixed；
(2) above-mentioned mixed solution is warming up to 90 °C, stirring evaporation is done then in 90 °C of dry 10 h of drying box
Gel；
(3) it will be put into crucible after the grinding of above-mentioned xerogel, 650 °C of 36 h of calcining, then cooled to room temperature, obtains
Piezoelectric material Li2GeO3The nickelic positive electrode of cladding.
Embodiment 11
Piezoelectric material LiTaO3And BaTiO3Coated lithium ion battery lithium-rich anode material Li1.2Mn0.56Ni0.17Co0.07O2。
Configure the Ta of 0.1 M2O5、C4H6O6And CH3COOLi is dissolved in ethanol solution, is proportionally chosen, and is instilled
It is dissolved in the positive electrode solution in ethyl alcohol, 8 h is then mixed；
(2) above-mentioned mixed solution is warming up to 100 °C, stirring evaporation obtains then in 120 °C of dry 12 h of drying box
Xerogel；
(3) it will be put into crucible after the grinding of above-mentioned xerogel, 500 °C of 48 h of calcining, cooled to room temperature obtains piezoelectricity
Material LiTaO3The lithium-rich anode material of cladding.
(4) Ba of 0.1 M is configured2CO3、C6H8O7And C16H36CO4Ti is dissolved in ethanol solution, is proportionally chosen, will
It instills the above-mentioned composite material being dissolved in ethyl alcohol, and 10 h are then mixed；
(5) above-mentioned mixed solution is warming up to 80 °C, stirring evaporation is done then in 80 °C of dry 12 h of drying box
Gel；
(6) it will be put into crucible after the grinding of above-mentioned xerogel, 600 °C of 7 h of calcining, then cooled to room temperature, is pressed
Electric material LiTaO3And BaTiO3The lithium-rich anode material of dual cladding.
Embodiment 12
Piezoelectric material LiNbO3、LiTaO3And BaTiO3Triple coated lithium ion battery lithium cobaltate cathode material LiCoO2。
(1) Ba of 0.1 M is configured2CO3、C6H8O7And C16H36CO4Ti is dissolved in ethanol solution, is proportionally chosen, will
It is instilled in the positive electrode solution being dissolved in ethyl alcohol, and 10 h are then mixed；
(2) above-mentioned mixed solution is warming up to 80 °C, stirring evaporation is done then in 80 °C of dry 12 h of drying box
Gel；
(3) it will be put into crucible after the grinding of above-mentioned xerogel, 800 °C of 9 h of calcining, then cooled to room temperature, is pressed
Electric material BaTiO3The lithium cobaltate cathode material of cladding；
(4) Ta of 0.1 M is configured2O5、C4H6O6And CH3COOLi is dissolved in ethanol solution, is proportionally chosen, and is instilled
The BaTiO being dissolved in ethyl alcohol3Then 8 h are mixed in the lithium cobaltate cathode material of cladding；
(5) Nb of 0.1 M is configured2O5、C4H6O6And CH3COOLi is dissolved in ethanol solution, is proportionally chosen, and is instilled
The above-mentioned mixed solution being dissolved in ethyl alcohol, is then mixed 8 h；
(6) above-mentioned mixed solution is warming up to 120 °C, stirring evaporation obtains then in 120 °C of dry 12 h of drying box
Xerogel；
(7) it will be put into crucible after the grinding of above-mentioned xerogel, 500 °C of 48 h of calcining, cooled to room temperature obtains piezoelectricity
Material LiNbO3、LiTaO3And BaTiO3The lithium cobaltate cathode material of triple claddings.
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
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of anode material for lithium-ion batteries of surface cladding piezoelectric material, it is characterised in that: cell positive material surface packet
One layer of piezoelectric material with piezoelectric effect is covered.
2. the anode material for lithium-ion batteries of cladding piezoelectric material in surface according to claim 1, it is characterised in that: described
Piezoelectric material includes any one of barium titanate, lithium niobate, sodium niobate, lithium tantalate, inclined potassium-sodium niobate and inclined strontium barium niobate or more
Kind.
3. the anode material for lithium-ion batteries of cladding piezoelectric material in surface according to claim 1, it is characterised in that: described
Cell positive material is cobalt acid lithium, lithium nickelate and the derivative of layer structure；Ternary layered material, rich lithium ternary material and derivative
Object；Spinel structure Li-Ni-Mn-O, LiMn2O4 and derivative；Olivine structure lithium iron phosphate and derivative.
4. the anode material for lithium-ion batteries of cladding piezoelectric material in surface according to claim 1, it is characterised in that: described
Piezoelectric material accounts for 0.1 wt. % -5 wt. % of cell positive material quality.
5. the preparation method of the anode material for lithium-ion batteries of the described in any item surface cladding piezoelectric materials of claim 1-4,
It is characterized by the following steps:
(1) piezoelectric material presoma is dissolved in acid solution, obtains finely dispersed piezoelectric material presoma through strong stirring
Mixed solution；
(2) in a solvent by anode active material of lithium ion battery dispersion, agitated to obtain evenly dispersed dispersion liquid；
(3) piezoelectric material precursor mixed solution obtained in step (1) is mixed with dispersion liquid obtained in step (2), is passed through
Strong stirring obtains homogeneous mixture solotion；
(4) the homogeneous mixture solotion evaporation ageing obtained step (3), obtains anode active material of lithium ion battery and piezoresistive material
Material precursor complex sol, complex sol is sufficiently dry, form xerogel；
(5) xerogel obtained by step (4) is fully ground, obtained after annealed processing the lithium of coated with uniform piezoelectric material from
Sub- cell positive material.
6. the preparation method of the anode material for lithium-ion batteries of cladding piezoelectric material in surface according to claim 5, special
Sign is: piezoelectric material presoma is in nitrate, acetate, ethylate or the oxide of piezoelectric material in the step (1)
Any one；Acid solution is the ethanol solution of citric acid or tartaric acid, and the concentration of mixed solution is 1.0g/L-2.0g/L.
7. the preparation method of the anode material for lithium-ion batteries of cladding piezoelectric material in surface according to claim 5, special
Sign is: piezoelectric material presoma and the mass ratio of anode active material of lithium ion battery in step (2) are in the step (1)
(0.001-0.05): 1.
8. the preparation method of the anode material for lithium-ion batteries of cladding piezoelectric material in surface according to claim 5, special
Sign is: the temperature of evaporation ageing is 60-120 DEG C in the step (4), and drying temperature is 80-120 DEG C, time 10-12h.
9. the preparation method of the anode material for lithium-ion batteries of cladding piezoelectric material in surface according to claim 5, special
Sign is: annealing temperature is 500-900 DEG C in the step (5), annealing time 6-48h.
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