CN102956895A - Surface composite coated anode material, preparation method thereof and lithium ion battery - Google Patents
Surface composite coated anode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN102956895A CN102956895A CN2012104612991A CN201210461299A CN102956895A CN 102956895 A CN102956895 A CN 102956895A CN 2012104612991 A CN2012104612991 A CN 2012104612991A CN 201210461299 A CN201210461299 A CN 201210461299A CN 102956895 A CN102956895 A CN 102956895A
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- Prior art keywords
- lithium
- intercalation compound
- phosphate
- lithium intercalation
- anode material
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- Granted
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000010405 anode material Substances 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 230000002687 intercalation Effects 0.000 claims abstract description 34
- 238000009830 intercalation Methods 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910017119 AlPO Inorganic materials 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 11
- 230000006798 recombination Effects 0.000 claims description 8
- 238000005215 recombination Methods 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000011833 salt mixture Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000011029 spinel Chemical group 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010450 olivine Substances 0.000 claims description 3
- 229910052609 olivine Inorganic materials 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 19
- 238000000576 coating method Methods 0.000 abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000008961 swelling Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910003900 Li(Ni0.5Co0.2Mn0.3)O2 Inorganic materials 0.000 description 2
- 229910012399 LiCo0.998Mg0.002O2 Inorganic materials 0.000 description 2
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910015030 LiNiCoO Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006258 conductive agent Substances 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
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a surface composite coated lithium ion battery anode material, a preparation method thereof and a lithium ion battery. The anode material comprises a lithium intercalation compound basal body and an Al2O3-AlPO4 composite layer which is coated on the basal body. The mass ratio of Al elements to lithium intercalation compounds is 0.04-0.15 percent. The mass percent of Al2O3 in the composite layer is 10-90 percent. The preparation method comprises the following steps of: dissolving easily soluble aluminum salt in solvent to form solution A; dissolving easily soluble alkaline substances and easily soluble phosphate in solvent to form solution B; dispersing the lithium intercalation compounds in a dispersing medium to obtain a dispersion system M; enabling the solution B and the solution A to form sol substances, adding the sol substances into the dispersion system M and enabling sol particles to be evenly adsorbed on the surfaces of the lithium intercalation compounds; and finally conducting solid-liquid separation and subsequent treatment. By adopting the technical scheme, the defects of sole coating can be effectively overcome, and the lithium ion battery with excellent rate capability and high-temperature circulating performance can be prepared.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to anode material for lithium-ion batteries and its preparation method that a kind of surface recombination coats, and the lithium ion battery that adopts this positive electrode.
Background technology
Lithium ion battery has the advantages that as a kind of novel secondary cell specific capacity is high, voltage is high, fail safe is good, is widely used in portable type electronic product.Anode material for lithium-ion batteries commonly used has LiCoO
2, LiNiCoO
2, LiNiCoMnO
2And LiMn
2O
4Deng.The researcher of various countries is also at exploitation high voltage material, for example LiNi at present
0.5Mn
1.5O
4, LiCoPO
4Deng.Along with the continuous upgrading of electronic product, market demand improves constantly the volume energy density of battery, and therefore anode material for lithium-ion batteries commonly used also is applied to the high-voltage battery scope gradually, for example with LiCoO
2Be applied to 3 ~ 4.35V.
No matter be the high-voltage lithium ion battery cathode material of developing, or anode material for lithium-ion batteries commonly used, they are faced with a common problem under Charging state: electrolyte is had stronger oxidizability, easy and electrolyte reacts, cause positive electrode itself destructurized on the one hand, also can cause security incident on the other hand.Therefore, need to carry out the surface to these materials and coat processing: coat one deck non-electrochemical active material on the positive electrode surface, under the prerequisite of not losing the positive electrode specific capacity, stop positive electrode to contact with the direct of electrolyte, thereby improve the structural stability of positive electrode, improve security performance and the high temperature charge and discharge cycles stability of lithium ion battery.
At present, patent documentation and Research Literature provide positive electrode of kinds of surface coating and preparation method thereof, utilize aluminum soluble salt and water soluble alkali reaction to generate aluminium colloidal sol such as Chinese patent CN 101950803A, then mix with positive electrode, finally prepared the positive electrode of surface-coated aluminum oxide.Because aluminium oxide is a kind of insulating material, electron conduction and ionic conductivity are all bad, so the high rate performance of the anode material for lithium-ion batteries of alumina-coated can decrease.(the Control of AlPO of Jaephil Cho seminar
4-nanoparticle coating on LiCoO
2Byusing water or ethanol; 4182-4187) and (the Suppression of structural degradation of LiNi of Donggi Ahn seminar Electrochimica Acta 50(2005)
0.9Co
0.1O
290 ° of C byAlPO of cathode at
4-nanoparticle coating; Current Applied Physics 7(2007) 172-175) all introduced the performance of the positive electrode of the method for aluminum phosphate clad anode material and coating.Utilize the aluminum phosphate clad anode material, can improve the high rate performance of positive electrode, but the high temperature cyclic performance aspect is still waiting to improve.
Summary of the invention
An object of the present invention is for the problems referred to above, all anode material for lithium-ion batteries of excellent surface recombination coating of a kind of high rate performance and high temperature cyclic performance are provided, with and preparation method thereof.
The anode material for lithium-ion batteries that surface recombination of the present invention coats comprises lithium intercalation compound matrix and the Al that is coated on this matrix surface
2O
3-AlPO
4Composite bed; Al element in this composite bed and the mass ratio of described lithium intercalation compound are 0.04% ~ 0.15%; At Al
2O
3-AlPO
4Al in the composite bed
2O
3Mass fraction be 10% ~ 90%.
Further, described lithium intercalation compound is one or more the mixture in layer structure lithium intercalation compound, spinel structure lithium intercalation compound, the olivine structural lithium intercalation compound.
The preparation method of the anode material for lithium-ion batteries that surface recombination of the present invention coats may further comprise the steps:
(1) easy molten aluminium salt is dissolved in forms solution A in the solvent;
(2) easy molten alkaline matter is mixed with easy molten phosphate, be dissolved in and form solution B in the solvent;
(3) under stirring state, with the pH value of solution B regulator solution A, make it form colloidal sol shape material;
(4) with lithium intercalation compound dispersed with stirring in decentralized medium, obtain disperse system M;
(5) described colloidal sol shape material is joined among the disperse system M, make sol particle evenly be adsorbed in the surface of lithium intercalation compound;
(6) Separation of Solid and Liquid obtains the lithium intercalation compound that adsorption has sol particle;
(7) adsorption is had the lithium intercalation compound of sol particle dry, roasting, form the surface and be coated with Al
2O
3-AlPO
4The anode material for lithium-ion batteries of composite bed.
In the step (1), described easy molten aluminium salt is one or more the salt-mixture in nitrate, sulfate, acetate, the halide.
In the step (2), described easy molten alkaline matter is one or more the mixture in hydroxide, basic anhydride, carbonate, the ammoniacal liquor, and described easy molten phosphate is one or more the salt-mixture in phosphoric acid one hydrogen lithium, lithium dihydrogen phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate and the potassium dihydrogen phosphate.
In step (1) and the step (2), described solvent is one or both the mixture in water, the organic solvent.
In the step (3), the adjustable range of described pH value is 4.0 ~ 7.0.
In the step (4), described decentralized medium is one or both the mixture in water, the organic solvent.
In the step (7), described sintering temperature is 400 ~ 900 ℃, and roasting time is 3 ~ 7 hours.
Another object of the present invention provides a kind of lithium ion battery, comprises positive pole, negative pole, barrier film and electrolyte, wherein: described positive pole just very provided by the present invention; Described negative pole comprises collector and the negative material that loads on the collector; Described barrier film places between positive pole and the negative pole, has electronic isolation and Li ion conduction property; Described electrolyte is comprised of nonaqueous solvents, electrolyte lithium salt and film for additive.
The present invention is by carrying out Al to the lithium intercalation compound matrix surface
2O
3-AlPO
4Compound coating is with independent employing Al
2O
3Coat or adopt separately AlPO
4Coating is compared, the shortcoming that exists in the time of can effectively overcoming independent the coating.Adopt the anode material for lithium-ion batteries of the surface recombination coating of the present invention's preparation can obtain high rate performance and the equal excellent lithium ion battery of high temperature cyclic performance.
Description of drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the anode material for lithium-ion batteries of embodiment 1 preparation.
Fig. 2 is the transmission electron microscope picture of the anode material for lithium-ion batteries of embodiment 1 preparation.
Fig. 3 is the high rate performance curve under the anode material for lithium-ion batteries room temperature of embodiment 2 preparation.
Fig. 4 is that the anode material for lithium-ion batteries of embodiment 2 preparation is at 45 ℃ cycle performance curve.
Embodiment
Below by embodiment, and cooperate accompanying drawing, the present invention is further described.
Experiment will adopt CR 2430 type button cells and 454261 type flexible packing lithium ion batteries to study the chemical property of positive electrode of the present invention.
The anodal NMP that adopts is as solvent, by active material: SP: PVDF=94: be mixed with solid content at 3: 3 and be 70% slurry and evenly be coated on the Al paper tinsel.
Negative pole adopts deionized water as solvent, by graphite: SP: SBR: CMC=90: be mixed with solid content at 4: 3: 3 and be 45% slurry evenly on the Cu paper tinsel.
Electrolyte is the LiPF6 solution of 1mol/L, and solvent is the mixed solvent of EC, DEC and EMC, and volume ratio is 1: 1: 1.
The negative pole of button cell uses the Li sheet, anodal use pole piece of the present invention.In the glove box of argon shield, positive pole, negative pole, electrolyte, barrier film and battery case are assembled into button cell.
Positive pole, negative pole and the barrier film made are wound into battery core, through entering shell, closedtop, fluid injection, change into, the master operations such as moulding, detection make 454261 type finished product flexible-packed batteries.First with the 1C constant current battery is charged to 4.5V at normal temperatures during the test of 85 ℃/4h of battery high temperature storage, constant voltage left standstill 1 hour to 0.05C, measure cell thickness, voltage is after the internal resistance size, put it in 85 ℃ the insulating box, left standstill detect thickness at high temperature, voltage 4 hours, internal resistance is cooled to normal temperature:
Thickness * 100% before high temperature storage thickness swelling=(thickness before thickness after the storage-storage)/storage.
Embodiment 1:
Take by weighing 2.09g Al (NO
3)
39H
2O is dissolved in the 20mL water; Take by weighing 0.45g NaOH and 0.21g (NH
4)
2HPO
4, mix, be dissolved in the 20mL water; With NaOH and (NH
4)
2HPO
4The solution that forms slowly is added drop-wise to Al (NO
3)
39H
2In the O solution, pH is 4.5 in control, obtains colloidal sol; Take by weighing 200g layer structure lithium intercalation compound cobalt acid lithium sample, add 120mL water as decentralized medium, carry out dispersed with stirring; The colloidal sol that forms is slowly joined in the cobalt acid lithium sample of dispersed with stirring reaction 2h; Leave standstill, filter, with the filter cake oven dry that obtains; With the oven dry material at 550 ℃ of lower roasting 5h, obtain Al
2O
3-AlPO
4The lithium cobaltate cathode material of compound coating, wherein the mass percent of Al element and cobalt acid lithium is 0.075%; At Al
2O
3-AlPO
4Al in the composite bed
2O
3The quality that accounts for is 51.14% than mark.
To the Al that obtains
2O
3-AlPO
4The lithium cobaltate cathode material of compound coating carries out scanning electron microscopic observation, the results are shown in accompanying drawing 1.To the Al that obtains
2O
3-AlPO
4The lithium cobaltate cathode material of compound coating carries out transmission electron microscope observing, the results are shown in accompanying drawing 2.
Above-mentioned positive electrode is 8% at 85 ℃/4h of 454261 soft-package batteries high temperature storage thickness swelling.
Embodiment 2:
Take by weighing 1.65g Al
2(SO4)
3Be dissolved in the 20mL water; Take by weighing 0.55g KOH and 0.19g (NH
4)
2HPO
4, mix, be dissolved in the 20mL water; With KOH and (NH
4)
2HPO
4The solution that forms slowly is added drop-wise to Al
2(SO4)
3In the solution, pH is 7.0 in control, obtains colloidal sol; Take by weighing 200g layer structure lithium intercalation compound cobalt acid lithium sample, add 120mL water as decentralized medium, carry out dispersed with stirring; The colloidal sol that forms is added drop-wise in the cobalt acid lithium sample of dispersed with stirring reaction 2h; Leave standstill, filter, with the filter cake oven dry that obtains; With the oven dry material at 650 ℃ of lower roasting 5h, obtain Al
2O
3-AlPO
4The lithium cobaltate cathode material of compound coating, wherein the mass percent of Al element and cobalt acid lithium is 0.065%, at Al
2O
3-AlPO
4Al in the composite bed
2O
3The quality that accounts for is 70% than mark.
Al with preparation
2O
3-AlPO
4The lithium cobaltate cathode material of compound coating is anodal, and acetylene black is conductive agent, and polytetrafluoroethylene is binding agent, makes electrode slice, take lithium metal as reference electrode, is assembled into the simulation button cell.
Above-mentioned positive electrode is in CR2430 type button cell, at room temperature, 3 ~ 4.5V carries out high rate performance test, the results are shown in accompanying drawing 3.Can find out 1C/0.1C=96%, 2C/0.1C=93%.
Above-mentioned positive electrode between 45 ℃, 3 ~ 4.5V, charges and discharge loop test with 0.7C/0.7C in 454261 soft-package batteries, the results are shown in accompanying drawing 4.Can find out, capability retention is 95% after the circulation of 100 weeks.
Above-mentioned positive electrode is 5% at 85 ℃/4h of 454261 soft-package batteries high temperature storage thickness swelling.
Embodiment 3:
Take by weighing 2.03g Al
2(SO
4)
3Be dissolved in the 20mL water; Take by weighing 0.67g KOH and 0.45g K
2HPO
4, mix, be dissolved in the 20mL water; With KOH and K
2HPO
4The solution that forms slowly is added drop-wise to Al
2(SO
4)
3In the solution, pH is 4.8 in control, obtains colloidal sol; Take by weighing 200g layer structure lithium intercalation compound Li (Ni
0.5Co
0.2Mn
0.3) O
2Cell positive material adds 120mL water as decentralized medium, carries out dispersed with stirring; The colloidal sol that forms is added drop-wise in the cobalt acid lithium sample of dispersed with stirring reaction 3h; Leave standstill, filter, with the filter cake oven dry that obtains; With the oven dry material at 800 ℃ of lower roasting 5h, obtain Al
2O
3-AlPO
4Li (the Ni of compound coating
0.5Co
0.2Mn
0.3) O
2Anode material for lithium-ion batteries, wherein Al element and lithium intercalation compound Li (Ni
0.5Co
0.2Mn
0.3) O
2Mass percent be 0.080%, at Al
2O
3-AlPO
4Al in the composite bed
2O
3The quality that accounts for is 60% than mark.
Above-mentioned positive electrode is 10% at 85 ℃/4h of 454261 soft-package batteries high temperature storage thickness swelling.
Embodiment 4:
Take by weighing 1.27g Al
2(SO
4)
3Be dissolved in the 20mL water; Take by weighing 0.52g K
2CO
3With 0.28g K
2HPO
4, mix, be dissolved in the 20mL water; With K
2CO
3And K
2HPO
4The solution that forms slowly is added drop-wise to Al
2(SO
4)
3In the solution, pH is 4.0 in control, obtains colloidal sol; Take by weighing 200g spinel structure lithium intercalation compound LiNi
0.5Mn
1.5O
4Cell positive material adds 120mL water as decentralized medium, carries out dispersed with stirring; The colloidal sol that forms is added drop-wise in the cobalt acid lithium sample of dispersed with stirring reaction 3h; Leave standstill, filter, with the filter cake oven dry that obtains; With the oven dry material at 700 ℃ of lower roasting 3h, obtain Al
2O
3-AlPO
4The LiNi of compound coating
0.5Mn
1.5O
4Anode material for lithium-ion batteries, wherein Al element and spinel structure lithium intercalation compound LiNi
0.5Mn
1.5O
4Mass percent be 0.050%, at Al
2O
3-AlPO
4Al in the composite bed
2O
3The quality that accounts for is 60% than mark.
Above-mentioned positive electrode is 15% at 85 ℃/4h of 454261 soft-package batteries high temperature storage thickness swelling.
Embodiment 5:
Take by weighing 0.61gA1 (CH
3COO)
3Be dissolved in the 20mL water; Take by weighing 0.09g Na
2O and 0.02g (NH
4)
2HPO
4, mix, be dissolved in the 20mL water; With Na
2O and (NH
4)
2HPO
4The solution that forms slowly is added drop-wise to A1 (CH
3COO)
3In the solution, pH is 6.5 in control, obtains colloidal sol; Take by weighing 200g layer structure lithium intercalation compound LiCo
0.998Mg
0.002O
2Sample adds 120mL water as decentralized medium, carries out dispersed with stirring; The colloidal sol that forms is added drop-wise in the cobalt acid lithium sample of dispersed with stirring reaction 2h; Leave standstill, filter, with the filter cake oven dry that obtains; With the oven dry material at 900 ℃ of lower roasting 5h, obtain Al
2O
3-AlPO
4The LiCo of compound coating
0.998Mg
0.002O
2Positive electrode, wherein Al element and layer structure lithium intercalation compound LiCo
0.998Mg
0.002O
2Mass percent be 0.04%, at Al
2O
3-AlPO
4Al in the composite bed
2O
3The quality that accounts for is (90%) than mark.
Above-mentioned positive electrode is 8% at 85 ℃/4h of 454261 soft-package batteries high temperature storage thickness swelling.
Embodiment 6:
Take by weighing 1.48g AlCl
3Be dissolved in the mixed liquor of 30mL water and ethanol (volume ratio of water and ethanol is 2:1); Take by weighing 0.99g concentration and be 25% ammoniacal liquor and 1.53g K
2HPO
4, mix, be dissolved in the mixed liquor of 30mL water and ethanol (volume ratio of water and ethanol is 2:1); With ammoniacal liquor and K
2HPO
4The solution that forms slowly is added drop-wise to AlCl
3In the solution, pH is 5.5 in control, obtains colloidal sol; Take by weighing 200g olivine structural lithium intercalation compound LiFePO
4Cell positive material, the mixed liquor (volume ratio of water and ethanol is 2:1) that adds 120mL water and ethanol as decentralized medium, carries out dispersed with stirring; The colloidal sol that forms is added drop-wise in the cobalt acid lithium sample of dispersed with stirring reaction 3h; Leave standstill, filter, with the filter cake oven dry that obtains; With the oven dry material at 400 ℃ of lower roasting 7h, obtain Al
2O
3-AlPO
4The LiFePO of compound coating
4Anode material for lithium-ion batteries, wherein the mass content of Al is 0.15%, at Al
2O
3-AlPO
4Al in the composite bed
2O
3The quality that accounts for is 10% than mark.
Above-mentioned positive electrode is 5% at 85 ℃/4h of 454261 soft-package batteries high temperature storage thickness swelling.
Above-described embodiment is not construed as limiting the invention, and those skilled in the art can make various modifications or improvement according to basic thought of the present invention, only otherwise break away from basic thought of the present invention, and all within the scope of the present invention.
Claims (10)
1. the anode material for lithium-ion batteries that surface recombination coats is characterized in that, comprises lithium intercalation compound matrix and the Al that is coated on this matrix surface
2O
3-AlPO
4Composite bed; Al element in this composite bed and the mass ratio of described lithium intercalation compound are 0.04% ~ 0.15%; Al in this composite bed
2O
3Mass fraction be 10% ~ 90%.
2. anode material for lithium-ion batteries as claimed in claim 1 is characterized in that: described lithium intercalation compound is one or more the mixture in layer structure lithium intercalation compound, spinel structure lithium intercalation compound, the olivine structural lithium intercalation compound.
3. the preparation method of the anode material for lithium-ion batteries that coats of a surface recombination, its step comprises:
(1) easy molten aluminium salt is dissolved in forms solution A in the solvent;
(2) easy molten alkaline matter is mixed with easy molten phosphate, be dissolved in and form solution B in the solvent;
(3) with the pH value of solution B regulator solution A, make it form colloidal sol shape material;
(4) lithium intercalation compound is disperseed in decentralized medium, obtain disperse system M;
(5) described colloidal sol shape material is joined among the disperse system M, make sol particle evenly be adsorbed in the surface of lithium intercalation compound;
(6) Separation of Solid and Liquid obtains the lithium intercalation compound that adsorption has sol particle;
(7) the gained lithium intercalation compound is dry, roasting forms the surface and is coated with Al
2O
3-AlPO
4The anode material for lithium-ion batteries of composite bed.
4. method as claimed in claim 3 is characterized in that: described easy molten aluminium salt is one or more the salt-mixture in nitrate, sulfate, acetate, the halide.
5. method as claimed in claim 3 is characterized in that: described easy molten alkaline matter is one or more the mixture in hydroxide, basic anhydride, carbonate, the ammoniacal liquor; Described easy molten phosphate is one or more the salt-mixture in lithium phosphate, phosphoric acid one hydrogen lithium, lithium dihydrogen phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate and the potassium dihydrogen phosphate.
6. method as claimed in claim 3 is characterized in that: step (1) and the described solvent of step (2) are one or both the mixture in water, the organic solvent; The described decentralized medium of step (4) is one or both the mixture in water, the organic solvent.
7. method as claimed in claim 3, it is characterized in that: the adjustable range of the described pH value of step (3) is 4.0 ~ 7.0.
8. method as claimed in claim 3, it is characterized in that: the temperature of the described roasting of step (7) is 400 ~ 900 ℃, and the time is 3 ~ 7 hours.
9. a lithium ion battery is characterized in that: its anodal claim 1 or 2 described positive electrodes of adopting.
10. lithium ion battery as claimed in claim 9 is characterized in that: comprise described positive pole and negative pole, barrier film and electrolyte, described negative pole comprises collector and loads on negative material on the collector; Described barrier film places between positive pole and the negative pole, has electronic isolation and Li ion conduction property; Described electrolyte is comprised of nonaqueous solvents, electrolyte lithium salt and film for additive.
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