CN105280910A - Phosphorus-contained lithium ion battery positive electrode material and preparation method therefor - Google Patents
Phosphorus-contained lithium ion battery positive electrode material and preparation method therefor Download PDFInfo
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- CN105280910A CN105280910A CN201410329763.0A CN201410329763A CN105280910A CN 105280910 A CN105280910 A CN 105280910A CN 201410329763 A CN201410329763 A CN 201410329763A CN 105280910 A CN105280910 A CN 105280910A
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- lithium
- composite oxide
- oxide particle
- anode material
- ion batteries
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 title abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 44
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 20
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000011247 coating layer Substances 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 nickel aluminum cobalt Chemical compound 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 41
- 239000010405 anode material Substances 0.000 claims description 25
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 21
- 229910017052 cobalt Inorganic materials 0.000 claims description 20
- 239000010941 cobalt Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 238000009938 salting Methods 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 6
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052768 actinide Inorganic materials 0.000 claims description 6
- 150000001255 actinides Chemical class 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 6
- 150000002602 lanthanoids Chemical class 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910052714 tellurium Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 28
- 238000000034 method Methods 0.000 abstract description 7
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 5
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical class [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 abstract 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 abstract 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- 229910013733 LiCo Inorganic materials 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 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)
Abstract
The invention discloses a phosphorus-contained lithium ion battery positive electrode material and a preparation method therefor. The lithium battery positive electrode material of the invention comprises a composite oxide core and a coating layer; the core is single or doped modified ternary materials such as lithium cobalt oxides, nickel manganese cobalt or nickel aluminum cobalt, lithium manganate, lithium iron phosphate, lithium-rich manganese base and the like; and the coating layer is high-molecular polymer containing phosphorus oxygen bonds. The preparation process of the composite lithium battery positive electrode material is simple in method, easy to control the process, and convenient to realize industrial production.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, be specifically related to a kind of phosphorous anode material for lithium-ion batteries and preparation method thereof.
Background technology
The advantages such as lithium ion battery is high with its specific discharge capacity, fail safe good, have extended cycle life, are widely used in the portable type electronic product such as camera, mobile phone and the field such as electric vehicle and large-sized power power supply.The performance of lithium ion battery depends primarily on the positive electrode of lithium ion battery, positive electrode current material mainly contains cobalt acid lithium, nickel cobalt manganese or nickel cobalt aluminium ternary material, LiFePO 4 and LiMn2O4 etc., but this several positive electrode has the defect of self, such as cobalt acid lithium is expensive, overcharge resistance performance is poor, and the gram volume under 4.2V plays limited; Nickel cobalt manganese or nickel cobalt aluminium ternary material exist compacted density low, with the poor compatibility of electrolyte and the easy problem such as flatulence; The high temperature circulation of LiMn2O4 and high-temperature storage performance are not good; Then there is the problem such as poor performance at low temperatures and homogeneity of product difference in LiFePO4.In order to address these problems, surface coating technology is the means commonly used the most and approve, Surface coating can improve the surface texture stability of positive electrode, improves the cycle performance under battery high voltage.Lot of domestic and international document adopts Al with patent reports
2o
3, AlPO
4, ZrO
2, TiO
2, B
2o
3deng the technology of oxide clad anode material, although the cycle performance of coated rear material makes moderate progress, actual effect of improving is very limited, also can reduce the gram volume and discharge voltage plateau etc. of positive electrode.
Therefore need a kind of positive electrode, under itself institute's tool superiority condition of guarantee, obtain better circulation, high temperature storage, cryogenic property etc.
Summary of the invention
An object of the present invention is to provide a kind of phosphorous anode material for lithium-ion batteries, and this material has high discharge capacity, high discharge voltage and high compacted density.
Another object of the present invention is to provide a kind of preparation method of above-mentioned phosphorous anode material for lithium-ion batteries.
For achieving the above object, the invention discloses a kind of phosphorous anode material for lithium-ion batteries, this anode material for lithium-ion batteries comprises: composite oxide particle kernel and the high molecular polymer coating layer containing phosphorus oxygen key.
Above-mentioned composite oxide particle kernel is the composite oxide particle at least comprising in lithium Li and nickel, cobalt Co or manganese Mn one or more; And this composite oxide particle has the average composition of following chemical formulation:
(chemical formula 1) Li
dni
aco
bmn
ce
1-a-b-co
2
Wherein, E represents at least one element be selected from Mn, Cr, Co, Ni, V, Ti, Al, Ga and Mg, and a, b, c, d meet following relationship: 0≤a≤1,0≤b≤1,0≤c≤1,0.4≤d≤1.5.
Preferably, above-mentioned composite oxide particle kernel can be single or ternary material such as the acid of the cobalt of doping vario-property lithium, nickel cobalt manganese or nickel cobalt aluminium etc., LiMn2O4, LiFePO4, lithium-rich manganese-based etc.
The above-mentioned high molecular polymer coating layer containing phosphorus oxygen key is one or more in phosphate or modified phosphate high molecular polymer; Preferably, be arranged at going up at least partially of the surface of composite oxide particle, there is on average forming by following chemical formulation:
(chemical formula 2) M
xoyP
2o
5zH
2o
M represents one or more that be selected from Li, Na, K, Zn, Co, Ni, Mn, Al, Mg, Ca, Cu, Fe, B, Si, Sn, Pb, Se, Te, Ti, Zr, Ba, Bi, Ge, Sc, group of the lanthanides or actinides, preferably, 0.3≤x≤3,0.1≤y≤2.
Above-mentioned anode material for lithium-ion batteries, preferably, the described inorganic polymer containing phosphorus oxygen key refers to and contains
,
,
,
or
deng one or more in the phosphate of phosphorus oxygen key or modified phosphate.
Above-mentioned phosphorous anode material for lithium-ion batteries, in described coating layer, the mass ratio of P elements and composite oxide particle kernel is 0.0001:1 ~ 0.5:1.
Preferably, above-mentioned phosphorous anode material for lithium-ion batteries, in described coating layer, the mass ratio of P elements and composite oxide particle kernel is 0.0009:1 ~ 0.3:1.
Above-mentioned anode material for lithium-ion batteries, preferably, the D of described composite oxide particle kernel
50scope is 5.0 ~ 20 μm.
On the other hand, for realizing object of the present invention, present invention also offers a kind of method preparing this phosphorous anode material for lithium-ion batteries: added by composite oxide particle in solution, suspension-turbid liquid or the colloidal sol containing phosphorus and form paste mixture, the mass ratio controlling composite oxide particle and solution is 0.05:1 ~ 0.75:1; Add again and react containing the M salting liquid of at least one in Li, Na, K, Zn, Co, Ni, Mn, Al, Mg, Ca, Cu, Fe, B, Sn, Pb, Se, Te, Ti, Zr, Ba, Bi, Ge, Sc, group of the lanthanides or actinides, form coating layer on composite oxide particle surface, the mass ratio controlling described element and composite oxide particle is 0 ~ 5000ppm; And controlling P elements in phosphorous salting liquid is 0.5:1 ~ 100:1 with the mass ratio of M element in the M salting liquid added again; Stir lower oven dry, heat treatment, obtains anode material for lithium-ion batteries.
Preparation method provided by the present invention specifically can also comprise following step:
(1) salt containing phosphorus is added to the water, stirs, form the phosphorous aqueous solution, suspension or colloidal sol.
(2) composite oxide particle to be covered is joined in above-mentioned solution, form paste mixture, the mass ratio controlling composite oxide particle and solution is 0.05:1 ~ 3:1, and the mass ratio controlling P elements and composite oxide particle in phosphorous salting liquid is 0.0001:1-0.5:1.
(3) add in said mixture and react containing the M salting liquid of at least one in Li, Na, K, Zn, Co, Ni, Mn, Al, Mg, Ca, Cu, Fe, B, Sn, Pb, Se, Te, Ti, Zr, Ba, Bi, Ge, Sc, group of the lanthanides or actinides, form coating layer on composite oxide particle surface, the mass ratio controlling M element and composite oxide particle in the above-mentioned M of adding salting liquid is 0 ~ 5000ppm; And controlling P elements in phosphorous salting liquid is 0.5:1 ~ 100:1 with the mass ratio of contained M element in the M salting liquid added again.
(4) dry under stirring.
(5) positive electrode of the inorganic phosphor-contained high molecular polymer of Surface coating is obtained after heat treatment.
In above-mentioned preparation method, described in step (1) containing the salt of phosphorus refer in the phosphate of phosphoric acid hydrogen root, dihydrogen phosphate or phosphate radical or modified phosphate one or more.
In above-mentioned preparation method, the composite oxide particle described in step (2) is the composite oxide particle at least comprising in lithium Li and nickel, cobalt Co or manganese Mn one or more; And this composite oxide particle has the average composition of following chemical formulation:
(chemical formula 1) Li
dni
aco
bmn
ce
1-a-b-co
2
Wherein, E represents at least one element be selected from Mn, Cr, Co, Ni, V, Ti, Al, Ga and Mg, and a, b, c, d meet following relationship: 0≤a≤1,0≤b≤1,0≤c≤1,0.4≤d≤1.5.
Preferably, above-mentioned composite oxide particle kernel can be single or ternary material such as the acid of the cobalt of doping vario-property lithium, nickel cobalt manganese or nickel cobalt aluminium etc., LiMn2O4, LiFePO4, lithium-rich manganese-based etc.
In above-mentioned preparation method, the water insoluble solution of composite oxide particle, suspension or colloidal sol described in step (2), both are solid solution mixing, and object is at the phosphorous compound of this composite oxide particle coated with uniform one deck.Further, can control the addition of this composite oxide particle, this composite oxide particle and the quality controllable of the aqueous solution, suspension or colloidal sol are made as 0.05:1 ~ 3:1.
In above-mentioned preparation method, the D of the composite oxide particle described in step (2)
50be preferably 5 ~ 20um.
In above-mentioned preparation method, preferably, in the phosphorous salting liquid described in step (2), the mass ratio of P elements and composite oxide particle is 0.0009:1 ~ 0.3:1.
In above-mentioned preparation method, the M salting liquid of at least one in Li, Na, K, Zn, Co, Ni, Mn, Al, Mg, Ca, Cu, Fe, B, Sn, Pb, Se, Te, Ti, Zr, Ba, Bi, Ge, Sc, group of the lanthanides or actinides described in step (3), be make solvent with water, the mass ratio of its addition and composite oxide particle to be covered is 0 ~ 0.05:1.
In above-mentioned preparation method, the salting liquid in step (3) joins in the paste mixture in step (2), and constantly stirs, and enables phosphorous solution, suspension or colloidal sol and the salting liquid that adds at this positive electrode material grains surface precipitation.
In above-mentioned preparation method, the process of step (5), one is make coating generate inorganic phosphor-contained high molecular polymer by high-temperature process reaction; Two is that coating is better combined in interface with positive active material, forms composite material, and removes residual solvent and the ion of other decomposable asymmetric choice net or volatilization.By this heat treatment, may interfacial diffusion be formed at coating and positive electrode active materials interface, cobalt atom is diffused in this inorganic phosphor-contained high molecular polymer coating layer.
In above-mentioned preparation method, at the heat treatment described in step (5) is preferably 600 DEG C ~ 1100 DEG C, process 0.5 ~ 10h.
The present invention can in positive electrode active materials material grains Surface Creation a layer thickness evenly and the inorganic phosphor-contained high molecular polymer coating layer of continuous print.This polymer covering layer refers to that phosphorous ion and the metal ion added form complex compound or other ionic compounds, and the content of wherein phosphorus is when being greater than the content of metal ion, form phosphorous inorganic polymer by dehydration, isomerization reaction, polymerization reaction or dehydrogenation reaction etc.This phosphorous high molecular polymer defines a kind of excellent diaphragm on cobalt acid lithium surface; this diaphragm can make ion pass through while the electron transfer between isolated electrolyte and active material; thus complete the embedding of lithium ion and while deviating from, avoiding electrolyte to decompose at higher voltages, therefore make this positive electrode can have better battery performance and capacity retention energy, high temperature storage and cryogenic property at higher voltages.
Accompanying drawing explanation
Accompanying drawing 1 is cycle performance figure under 4.5V half-cell 0.5C in embodiment 1.
Accompanying drawing 2 is cycle performance figure under 4.5V half-cell 0.5C in embodiment 2.
specific implementation method
embodiment 1
First 5.0g ammonium dihydrogen phosphate is dissolved in 250ml water, and joins in coated still; Secondly be the cation doping acid lithium (molecular formula: LiCo of 18.5 μm by average grain diameter
0.949zr
0.001mg
0.05o
2) 1200g joins in coated still, speed of agitator is 600r/min, stirs.Finally 12g aluminum nitrate is dissolved in 50ml water, joins in coated still.Open heating, dry while stirring.Cobalt acid lithium powder after oven dry is placed in after being warming up to 700 DEG C with the speed of 5 DEG C/min in box type furnace and keeps 6 hours, cross 300 mesh sieves after cooling to room temperature with the furnace, i.e. the sour lithium powder of the obtained cobalt coated by inorganic phosphor-contained high molecular polymer.This powder is rolled through batch mixing, slurrying, coating, oven dry, assembles, fluid injection, leave standstill change into aging partial volume after carry out 4.5V half-cell 0.5C charge-discharge test, cycle performance under test material high voltage; Carry out 1C discharge test under 4.4V half-cell ﹣ 20 DEG C of conditions, low-temperature characteristics under test material high voltage, and carry out the full battery of 4.4V 60 DEG C of * 7D0.5C charge-discharge tests, high-temperature storage characteristics under test material high voltage.Wherein under 4.4V half-cell ﹣ 20 DEG C of conditions, the 1C low temperature discharge time is 55min; The full battery of 4.4V 60 DEG C of * 7D high temperature storage battery bulging rates are 4.3%.
embodiment 2
First 20.0g polyphosphoric acids (PPA2) is dissolved in 250ml water, and joins in coated still; Secondly be the ternary material (molecular formula: LiNi of 13 μm by average grain diameter
0.5co
0.2mn
0.3o
2) 1000g joins in coated still, speed of agitator is 400r/min, stirs.Finally 3.5g Alumina gel and 0.5g magnesium carbonate are joined in coated still.Open heating, dry while stirring.Cobalt acid lithium powder after oven dry is placed in after being warming up to 900 DEG C with the speed of 5 DEG C/min in box type furnace and keeps 6 hours, cross 300 mesh sieves after cooling to room temperature with the furnace, i.e. the sour lithium powder of the obtained cobalt coated by inorganic phosphor-contained high molecular polymer.This powder is rolled through batch mixing, slurrying, coating, oven dry, assembles, fluid injection, leave standstill change into aging partial volume after carry out 4.5V half-cell 0.5C charge-discharge test, cycle performance under test material high voltage; Carry out 1C discharge test under 4.4V half-cell ﹣ 20 DEG C of conditions, low-temperature characteristics under test material high voltage, and carry out the full battery of 4.4V 60 DEG C of * 7D0.5C charge-discharge tests, high-temperature storage characteristics under test material high voltage.
embodiment 3
First 15.0g aluminium dihydrogen tripolyphosphate is dissolved in 250ml water, and joins in coated still; Secondly be the cation doping acid lithium (molecular formula: LiCo of 12 μm by average grain diameter
0.994ti
0.005zr
0.001o
2) 1000g joins in coated still, speed of agitator is 500r/min, stirs.Finally 2.0g ferric nitrate is dissolved in 80ml water, joins in coated still.Open heating, dry while stirring.Cobalt acid lithium powder after oven dry is placed in after being warming up to 800 DEG C with the speed of 5 DEG C/min in box type furnace and keeps 6 hours, cross 300 mesh sieves after cooling to room temperature with the furnace, i.e. the sour lithium powder of the obtained cobalt coated by inorganic phosphor-contained high molecular polymer.This powder is rolled through batch mixing, slurrying, coating, oven dry, assembles, fluid injection, leave standstill change into aging partial volume after carry out 4.5V half-cell 0.5C charge-discharge test, cycle performance under test material high voltage; Carry out 1C discharge test under 4.4V half-cell ﹣ 20 DEG C of conditions, low-temperature characteristics under test material high voltage, and carry out the full battery of 4.4V 60 DEG C of * 7D0.5C charge-discharge tests, high-temperature storage characteristics under test material high voltage.Wherein under 4.4V half-cell ﹣ 20 DEG C of conditions, the 1C low temperature discharge time is 60min; The full battery of 4.4V 60 DEG C of * 7D high temperature storage battery bulging rates are 2.5%.
embodiment 4
First 8.0g aluminium dihydrogen phosphate is dissolved in 250ml water, and joins in coated still; Secondly be the LiMn2O4 (molecular formula: LiMnO of 10 μm by average grain diameter
2) 1000g joins in coated still, speed of agitator is 600r/min, stirs.Finally 2.0g lanthanum nitrate is dissolved in 30ml water, joins in coated still.Open heating, dry while stirring.Cobalt acid lithium powder after oven dry is placed in after being warming up to 950 DEG C with the speed of 5 DEG C/min in box type furnace and keeps 6 hours, cross 300 mesh sieves after cooling to room temperature with the furnace, i.e. the sour lithium powder of the obtained cobalt coated by inorganic phosphor-contained high molecular polymer.This powder is rolled through batch mixing, slurrying, coating, oven dry, assembles, fluid injection, leave standstill change into aging partial volume after carry out 4.5V half-cell 0.5C charge-discharge test, cycle performance under test material high voltage; Carry out 1C discharge test under 4.4V half-cell ﹣ 20 DEG C of conditions, low-temperature characteristics under test material high voltage, and carry out the full battery of 4.4V 60 DEG C of * 7D0.5C charge-discharge tests, high-temperature storage characteristics under test material high voltage.
embodiment 5
First 3.0g aluminium dihydrogen phosphate is dissolved in 250ml water, and joins in coated still; Secondly be the cobalt acid lithium (molecular formula: LiCoO of 18.0 μm by average grain diameter
2) 1000g joins in coated still, speed of agitator is 600r/min, opens heating, dries while stirring.Cobalt acid lithium powder after oven dry is placed in after being warming up to 600 DEG C with the speed of 5 DEG C/min in box type furnace and keeps 6 hours, cross 300 mesh sieves after cooling to room temperature with the furnace, i.e. the sour lithium powder of the obtained cobalt coated by inorganic phosphor-contained high molecular polymer.This powder is rolled through batch mixing, slurrying, coating, oven dry, assembles, fluid injection, leave standstill change into aging partial volume after carry out 4.5V half-cell 0.5C charge-discharge test, cycle performance under test material high voltage; Carry out 1C discharge test under 4.4V half-cell ﹣ 20 DEG C of conditions, low-temperature characteristics under test material high voltage, and carry out the full battery of 4.4V 60 DEG C of * 7D0.5C charge-discharge tests, high-temperature storage characteristics under test material high voltage.
embodiment 6
First 18.08g ammonium dihydrogen phosphate is dissolved in 250ml water, and joins in coated still; Secondly be the lithium-rich manganese-based anode material (molecular formula: 0.6Li of 18.5 μm by average grain diameter
2mnO
30.4Li(Ni
0.55co
0.15mn
0.3) O
2) 1200g joins in coated still, speed of agitator is 600r/min, stirs.Finally 2.0g aluminum nitrate is dissolved in 250ml water, joins in coated still.Open heating, dry while stirring.Powder after oven dry is placed in after being warming up to 830 DEG C with the speed of 5 DEG C/min in box type furnace and keeps 6 hours, cross 300 mesh sieves after cooling to room temperature with the furnace, i.e. the obtained lithium-rich manganese-based powder coated by inorganic phosphor-contained high molecular polymer.This powder is rolled through batch mixing, slurrying, coating, oven dry, assembles, fluid injection, leave standstill change into aging partial volume after carry out 4.5V half-cell 0.5C charge-discharge test, cycle performance under test material high voltage; Carry out 1C discharge test under 4.4V half-cell ﹣ 20 DEG C of conditions, low-temperature characteristics under test material high voltage, and carry out the full battery of 4.4V 60 DEG C of * 7D0.5C charge-discharge tests, high-temperature storage characteristics under test material high voltage.
Claims (10)
1. a phosphorous anode material for lithium-ion batteries, this positive electrode comprises: composite oxide particle kernel and coating layer;
(1) composite oxide particle kernel, at least comprises one or more in lithium and nickel, cobalt or manganese;
(2) coating layer, is arranged at going up at least partially of the surface of above-mentioned composite oxide particle, at least comprises containing phosphorus oxygen key high molecular polymer.
2. phosphorous anode material for lithium-ion batteries according to claim 1, is characterized in that described composite oxides kernel has the average composition of following chemical formula expression:
(chemical formula 1) Li
dni
aco
bmn
ce
1-a-b-co
2
Wherein, E represents at least one element be selected from Mn, Cr, Co, Ni, V, Ti, Al, Ga and Mg, and 0≤a≤1,0≤b≤1,0≤c≤1,0.4≤d≤1.5.
3. phosphorous anode material for lithium-ion batteries according to claim 1, it is characterized in that described coating layer is for containing phosphorus oxygen key high molecular polymer, it has the average composition that following chemical general formula is expressed:
(chemical formula 2) M
xoyP
2o
5zH
2o
Wherein, M represents one or more that be selected from Li, Na, K, Zn, Co, Ni, Mn, Al, Mg, Ca, Cu, Fe, B, Si, Sn, Pb, Se, Te, Ti, Zr, Ba, Bi, Ge, Sc, group of the lanthanides or actinides, and 0.3≤x≤3,0.1≤y≤2.
4. phosphorous anode material for lithium-ion batteries according to claim 1, is characterized in that the mass ratio of P elements and composite oxide particle kernel in described coating layer is 0.0001:1 ~ 0.5:1.
5. anode material for lithium-ion batteries according to claim 1 and 2, is characterized in that the particle diameter of described composite oxide particle kernel is preferably 5 ~ 20um.
6. the preparation method of a phosphorous anode material for lithium-ion batteries, composite oxide particle is added in phosphorous salting liquid and forms paste mixture, the mass ratio controlling composite oxide particle and solution is 0.05:1 ~ 3:1, and the mass ratio controlling P elements and composite oxide particle in phosphorous salting liquid is 0.0001:1 ~ 0.1:1; Add again and react containing the M salting liquid of at least one in Li, Na, K, Zn, Co, Ni, Mn, Al, Mg, Ca, Cu, Fe, B, Sn, Pb, Se, Te, Ti, Zr, Ba, Bi, Ge, Sc, group of the lanthanides or actinides, form coating layer on composite oxide particle surface, the mass ratio controlling M element and composite oxide particle kernel is 0 ~ 5000ppm; Stir lower oven dry, heat treatment, obtains end product.
7. the preparation method of anode material for lithium-ion batteries according to claim 6, is characterized in that described composite oxide particle is the doping vario-property thing of cobalt acid lithium, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, LiMn2O4, lithium-rich manganese-based or above-mentioned substance.
8. the preparation method of anode material for lithium-ion batteries according to claim 6, is characterized in that in described phosphorous salting liquid, P elements is 0.5:1 ~ 100:1 with the mass ratio of contained M element in the M salting liquid added again.
9. the preparation method of anode material for lithium-ion batteries according to claim 6, is characterized in that one or more that described phosphorous salting liquid refers in the solution of phosphoric acid hydrogen root, dihydrogen phosphate, phosphate radical, suspension or colloidal sol.
10. the preparation method of anode material for lithium-ion batteries according to claim 6, it is characterized in that described heat treatment temperature is 600 DEG C ~ 1100 DEG C, the time is 0.5 ~ 10h.
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| CN106264849A (en) * | 2016-08-18 | 2017-01-04 | 孟玲 | It is precious that water is warmed up in the heating capable of circulation of a kind of charging property |
| CN107968200A (en) * | 2016-10-18 | 2018-04-27 | 北京当升材料科技股份有限公司 | A kind of lithium electricity positive electrode and preparation method thereof |
| CN108134077A (en) * | 2017-12-28 | 2018-06-08 | 清远佳致新材料研究院有限公司 | A kind of anode material for high-voltage lithium ion of nucleocapsid and preparation method thereof |
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| CN110518206A (en) * | 2019-08-22 | 2019-11-29 | 湖北锂诺新能源科技有限公司 | Manganese phosphate vanadium lithium and carbon coat the preparation method of nickel cobalt manganese aluminium composite positive pole altogether |
| CN111916712A (en) * | 2020-08-20 | 2020-11-10 | 南京理工大学 | Method for modifying surface of lithium cobaltate positive electrode material by phosphorus-containing compound and lithium cobaltate positive electrode material |
| CN111916712B (en) * | 2020-08-20 | 2022-04-22 | 南京理工大学 | Method for modifying surface of lithium cobaltate positive electrode material by phosphorus-containing compound and lithium cobaltate positive electrode material |
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Application publication date: 20160127 |