CN103474625A - Coating method for core-shell novel positive electrode material for lithium ion battery - Google Patents
Coating method for core-shell novel positive electrode material for lithium ion battery Download PDFInfo
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- CN103474625A CN103474625A CN201310335969XA CN201310335969A CN103474625A CN 103474625 A CN103474625 A CN 103474625A CN 201310335969X A CN201310335969X A CN 201310335969XA CN 201310335969 A CN201310335969 A CN 201310335969A CN 103474625 A CN103474625 A CN 103474625A
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- lithium
- ion batteries
- nucleocapsid structure
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- olivine
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000000576 coating method Methods 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 title abstract description 7
- 239000011258 core-shell material Substances 0.000 title abstract 4
- 239000000463 material Substances 0.000 claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000002738 chelating agent Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 11
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 9
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 8
- 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 claims description 8
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 229910015645 LiMn Inorganic materials 0.000 claims description 4
- 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 4
- 238000013019 agitation Methods 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 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 3
- 230000008569 process Effects 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 2
- ZSYNKHJUSDFTCQ-UHFFFAOYSA-N [Li].[Fe].P(O)(O)(O)=O Chemical compound [Li].[Fe].P(O)(O)(O)=O ZSYNKHJUSDFTCQ-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 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 coating method for a core-shell novel positive electrode material for a lithium ion battery. A uniform core-shell structure is formed by effective compounding two materials with electrochemical activity; and an effect for enhancing electrochemical performance of the materials is achieved by improving interface state of the materials and reducing side reactions. The coating method comprises the following steps of dispersing the positive electrode material for the lithium ion battery in deionized water and auxiliarily dispersing in a certain manner to obtain a slurry; dissolving a lithium source, an iron source, a phosphate radical source and a chelating agent in water; stirring for 1 hour at a room temperature to obtain a sol; adding the slurry obtained in the first step in the sol; adjusting a pH; then heating to a temperature of 80 DEG C; keeping the temperature for 1-12 h to form a gel; then drying the gel at a temperature of 100 DEG C; sintering the dry gel obtained by the former step for 1-10 hours at a temperature of 600-900 DEG C under the protection of nitrogen; and cooling to a room temperature naturally, so that the core-shell novel positive electrode material for the lithium ion battery is obtained.
Description
Technical field
The present invention relates to a kind of method of modifying of anode material for lithium-ion batteries, utilize the concept of nucleocapsid structure, adopt the method for collosol and gel, preparation has the Olivine-type Cathode Material in Li-ion Batteries of nucleocapsid structure.
Background technology
The development new energy materials is the research field that present state key is supported.As a kind of novel green storage battery, lithium ion battery is mainly used in portable type electronic product at present, also extensively as vehicle power, for electric automobile (EV) provides power, and, along with the further raising of material property, likely also play an important role in fields such as solar energy, wind energy electric power storage and peak load regulation networks future.The more anode material for lithium-ion batteries of research comprises the LiFePO4 of LiCoO2, LiNiO2, spinelle LiMn2O4 and olivine structural with layer structure at present.At present main several anode material for lithium-ion batteries all exist as LiNi1/3Co1/3Mn1/3O2, LiMn2O4 and LiNi0.5Mn1.5O4 the shortcoming that cycle performance descends under hot conditions, return its reason be mainly due to nickel, two kinds of elements of manganese in electrolyte, dissolve and Ni4+ to the strong oxidizing property effect of electrolyte, more side reaction occurs.The method that Chinese scholars mainly adopts oxide to coat at present solves above-mentioned shortcoming.
The disclosed high-voltage lithium ion battery cathode material preparation of patent CN102005563A and surface coating method; just nickel source He Meng source solution mixes with surfactant solution; drying again, in 350-450 ℃ of air, roasting obtains the precursor of Ni, Mn oxide; Precursor is mixed through the liquid phase ball milling with the lithium source, drying, in last air, 400-900 ℃ of roasting obtains positive electrode active materials; Add positive electrode active materials in the soluble aluminum salting liquid that contains the lithium source, control lithium source, soluble aluminum source, positive electrode active materials at suitable mole, fully be uniformly mixed, drying, high-temperature roasting is processed and is obtained the high voltage type anode material for lithium-ion batteries of end product for surface coating one deck lithium-containing transition metal oxide.
(the Journal of Power Sources such as Arrebola, 2010,195,4278 – 4284) by polymer, auxiliary method has been synthesized the spinelle LiNi0.5Mn1.5O4 material that the primary particle diameter is 80 nm, then itself and the mol ratio of zinc acetate according to 99:1 are dispersed in alcoholic solution, stir after 15 minutes and heat up and remove alcohol, then under the condition of 450 ℃, calcining obtains final clad material.They find, in little multiplying power, charge and discharge under condition, and treated LiNi0.5Mn1.5O4 material reveals more excellent chemical property than pure phase LiNi0.5Mn1.5O4 material list, and this is because the ZnO coated has intercepted the dissolving of Ni and Mn.But their this clad material, than under high magnification, can not show better performance.
Above traditional method for coating can increase the internal resistance of cell, and can not form coating layer on the surface of material fully uniformly.This patent provides a kind of new coating thinking, adopt the nucleocapsid structure model, method by two kinds of positive electrodes by collosol and gel combines, the LiFePO4 layer formed on the positive electrode surface can well reduce the content of nickel element, reduce the generation of side reaction, be conducive to the chemical property performance of material.In addition, such coating means can not reduce the energy density of electrode material, have more using value in actual production.
Summary of the invention
The preparation and the method for modifying that the purpose of this invention is to provide a kind of high-voltage anode material of lithium ion batteries, the material that the method makes is nucleocapsid structure, has effectively reduced the content of the nickel element of electrode material surface, has good chemical property.And this simple synthetic method, cost is low, and technique is simply controlled, is easy to suitability for industrialized production.
The technical solution used in the present invention is as follows:
A kind of Olivine-type Cathode Material in Li-ion Batteries method for coating of nucleocapsid structure comprises the following steps:
(1) anode material for lithium-ion batteries is dispersed in deionized water and in some way aid dispersion obtain slurry, control the solid content of slurry between 10%-60%;
(2) in molar ratio (1-1.05): 1:1:2 is soluble in water by lithium source, source of iron, phosphoric acid root and chelating agent, controls the pH value of solution between 5-9, controls the concentration of solution between 0.01mol/L-1mol/L, at room temperature stirs and within 1 hour, obtains colloidal sol;
(3) slurry in step (1) is slowly joined in above-mentioned colloidal sol and mechanical agitation makes it to mix, then rise to 80 ℃ of insulation 1-12h, make it to form gel, then this gel is dried under 100 ℃;
(4) by the xerogel that obtains in step (3) under the nitrogen atmosphere protection in 600-900 ℃ of calcining 1-10 hour, naturally cool to room temperature, obtain the anode material for lithium-ion batteries that the Novel phosphoric acid iron lithium of nucleocapsid structure coats.
Lithium ion battery electrode material described in step (1), for pressing the positive electrode that is greater than 3.5V in electric discharge, is selected from ternary material, LiCoO
2, LiMn
2o
4, LiNi
0.5mn
1.5o
4, one or more in rich lithium material.
Dispersing mode described in step (1) is that mechanical agitation is disperseed or ultrasonic dispersion.
Lithium source described in step (2) is one or more the mixture in lithium hydroxide, lithium nitrate, lithium acetate; Described source of iron is one or more in ferrous oxalate, ferric nitrate, ferric acetate, iron chloride, frerrous chloride; Described phosphoric acid root is one or more in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate; Described chelating agent is one or both the mixture in tartaric acid, citric acid.
Optimum sintering process described in step (4), for be warming up to 650 ℃ of insulations 8 hours with 5 ℃/min, cools to room temperature with the furnace.
The mass fraction of the LiFePO4 described in step (4) is controlled between 0.1-10%.
The particle size range of the LiFePO4 described in step (4) is controlled between 5-500nm.
Beneficial effect of the present invention:
(1) the present invention is different from the method that material in the past carries out finishing and mainly contains, and adopts the material with electro-chemical activity as shell, thereby increases energy and the power density of material, suppresses the side reaction occurred due to electro-catalysis;
(2) the present invention, for as core with as the material of shell, carrying out autotelic selection, can control effectively to the factor of the reduction material electrochemical behavior in electrochemical reaction process.Such as: suppress manganese ion dissolving, slow down Ni
4+to oxidation rate of electrolyte etc.;
(3) from the preparation method, sol-gel method can be realized the interionic mixing of clad material (shell), thereby the chemical uniformity of reinforcing material, and as the elements such as nickel manganese contained in bulk material (core) owing to itself thering is good complexing, can with colloidal sol in organic component, as: tartaric acid, citric acid etc. form weak chemical b `, thereby have realized the even coating of material.
Embodiment
Below in conjunction with embodiment, the present invention is described further, will further understand method of the present invention and advantage, but embodiment is only for understanding the present invention.
Embodiment 1
Get 0.1mol LiNi
1/3co
1/3mn
1/3o
2material, be dispersed in the 30ml deionized water by it and assisting ultrasonic disperses to obtain slurry.Take 0.005mol ferric nitrate, 0.005mol lithium nitrate, 0.005mol ammonium dihydrogen phosphate and 0.02mol citric acid and be dissolved in 200ml water, in stirring at room, within one hour, obtain colloidal sol.Again the slurry obtained is previously at the uniform velocity joined in colloidal sol, then be warming up to 80 ℃ and keep this temperature 10h, make it to form gel, then this gel is dried under 100 ℃; By the xerogel that obtains under the nitrogen atmosphere protection in 650 ℃ of calcinings 8 hours, naturally cool to room temperature, obtain nucleocapsid structure LiFePO
4@LiNi
1/3co
1/3mn
1/3o
2material; Adopting EC:EMC:DMC (1:1:1, V/V/V) is electrolyte, take lithium metal as negative pole is assembled into 2016 button cells, and recording 200 capability retentions of its 1C circulation on Land charge-discharge test instrument is 95%.
Embodiment 2
Get 0.1mol LiMn
2o
4material, be dispersed in the 30ml deionized water by it and assisting ultrasonic disperses to obtain slurry.Take 0.01mol ferric nitrate, 0.01mol lithium nitrate, 0.01mol ammonium dihydrogen phosphate and 0.02mol tartaric acid and be dissolved in 200ml water, in stirring at room, within one hour, obtain colloidal sol.Again the slurry obtained is previously at the uniform velocity joined in colloidal sol, then be warming up to 80 ℃ and keep this temperature 10h, make it to form gel, then this gel is dried under 100 ℃; By the xerogel that obtains under the nitrogen atmosphere protection in 600 ℃ of calcinings 8 hours, naturally cool to room temperature, obtain nucleocapsid structure LiFePO
4@LiMn
2o
4material; Adopt EC:EMC:DMC (1:1:1, V/V/V) be electrolyte, the lithium metal of take is assembled into 2016 button cells as negative pole, and on Land charge-discharge test instrument, to obtain its 0.2C first discharge specific capacity be 124.6mAh/g in test, and the 5C specific discharge capacity is 0.2C 94%.
Embodiment 3
Get 0.1mol LiNi
0.5mn
1.5o
4material, be dispersed in the 30ml deionized water by it and assisting ultrasonic disperses to obtain slurry.Take 0.005mol ferric phosphate, 0.005mol lithium nitrate and 0.02mol citric acid and be dissolved in 200ml water, in stirring at room, within one hour, obtain colloidal sol.Again the slurry obtained is previously at the uniform velocity joined in colloidal sol, then be warming up to 80 ℃ and keep this temperature 10h, make it to form gel, then this gel is dried under 100 ℃; By the xerogel that obtains under the nitrogen atmosphere protection in 650 ℃ of calcinings 8 hours, naturally cool to room temperature, obtain nucleocapsid structure LiFePO
4@LiNi
0.5mn
1.5o
4material; Adopting EC:EMC:DMC (1:1:1, V/V/V) be electrolyte, and the lithium metal of take is assembled into 2016 button cells as negative pole, and testing on Land charge-discharge test instrument and obtaining its 0.2C first discharge specific capacity is 133mAh/g, and the 5C specific discharge capacity is 0.2C 96%.
Embodiment 4
With the uncoated LiNi in embodiment 3
0.5mn
1.5o
4material is the contrast sample; Adopting EC:EMC:DMC (1:1:1, V/V/V) is electrolyte, and the lithium metal of take is assembled into 2016 button cells as negative pole, on Land charge-discharge test instrument, tests.Result shows that the material of uncoated modification is 81% at 100 capability retentions of 55 ℃ of lower 1C circulations; And the material through coating modification is 98% at 100 capability retentions of 55 ℃ of lower 1C circulations.
Claims (7)
1. the Olivine-type Cathode Material in Li-ion Batteries method for coating of a nucleocapsid structure is characterized in that comprising the following steps:
(1) anode material for lithium-ion batteries is dispersed in deionized water and in some way aid dispersion obtain slurry, control the solid content of slurry between 10%-60%;
(2) in molar ratio (1-1.05): 1:1:2 is soluble in water by lithium source, source of iron, phosphoric acid root and chelating agent, controls the pH value of solution between 5-9, controls the concentration of solution between 0.01mol/L-1mol/L, at room temperature stirs and within 1 hour, obtains colloidal sol;
(3) slurry in step (1) is slowly joined in above-mentioned colloidal sol and mechanical agitation makes it to mix, then rise to 80 ℃ of insulation 1-12h, make it to form gel, then this gel is dried under 100 ℃;
(4) by the xerogel that obtains in step (3) under the nitrogen atmosphere protection in 600-900 ℃ of calcining 1-10 hour, naturally cool to room temperature, obtain the anode material for lithium-ion batteries that the Novel phosphoric acid iron lithium of nucleocapsid structure coats.
2. the Olivine-type Cathode Material in Li-ion Batteries method for coating of nucleocapsid structure according to claim 1, is characterized in that, the lithium ion battery electrode material described in step (1), for pressing the positive electrode that is greater than 3.5V in electric discharge, is selected from ternary material, LiCoO
2, LiMn
2o
4, LiNi
0.5mn
1.5o
4, one or more in rich lithium material.
3. the Olivine-type Cathode Material in Li-ion Batteries method for coating of nucleocapsid structure according to claim 1, is characterized in that, the dispersing mode described in step (1) is that mechanical agitation is disperseed or ultrasonic dispersion.
4. the Olivine-type Cathode Material in Li-ion Batteries method for coating of nucleocapsid structure according to claim 1, is characterized in that, the lithium source described in step (2) is one or more the mixture in lithium hydroxide, lithium nitrate, lithium acetate; Described source of iron is one or more in ferrous oxalate, ferric nitrate, ferric acetate, iron chloride, frerrous chloride; Described phosphoric acid root is one or more in phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate; Described chelating agent is one or both the mixture in tartaric acid, citric acid.
5. the Olivine-type Cathode Material in Li-ion Batteries method for coating of nucleocapsid structure according to claim 1, is characterized in that, the optimum sintering process described in step (4), for be warming up to 650 ℃ of insulations 8 hours with 5 ℃/min, cools to room temperature with the furnace.
6. the Olivine-type Cathode Material in Li-ion Batteries method for coating of nucleocapsid structure according to claim 1, is characterized in that, the mass fraction of the LiFePO4 described in step (4) is controlled between 0.1-10%.
7. the Olivine-type Cathode Material in Li-ion Batteries method for coating of nucleocapsid structure according to claim 1, is characterized in that, the particle size range of the LiFePO4 described in step (4) is controlled between 5-500nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310335969.XA CN103474625B (en) | 2013-08-05 | 2013-08-05 | Novel lithium ion battery anode material coating method with core-shell structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310335969.XA CN103474625B (en) | 2013-08-05 | 2013-08-05 | Novel lithium ion battery anode material coating method with core-shell structure |
Publications (2)
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| CN103825026A (en) * | 2014-03-19 | 2014-05-28 | 中南大学 | Method for preparing lithium iron pyrophosphate used as positive material for lithium ion battery |
| CN103825001A (en) * | 2014-01-14 | 2014-05-28 | 深圳市振华新材料股份有限公司 | High-safety cathode material of lithium ion secondary battery as well as preparation method and application thereof in battery manufacture |
| CN104835985A (en) * | 2015-03-24 | 2015-08-12 | 江苏乐能电池股份有限公司 | A preparing method of a high-specific-energy lithium ion battery |
| CN105161705A (en) * | 2015-06-29 | 2015-12-16 | 山东玉皇新能源科技有限公司 | Lithium manganese phosphate-coated nickel-cobalt lithium manganate cathode material and preparation method thereof |
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| CN105161705A (en) * | 2015-06-29 | 2015-12-16 | 山东玉皇新能源科技有限公司 | Lithium manganese phosphate-coated nickel-cobalt lithium manganate cathode material and preparation method thereof |
| WO2017000741A1 (en) * | 2015-06-29 | 2017-01-05 | 山东玉皇新能源科技有限公司 | Lithium manganese phosphate-coated lithium nickel cobalt manganese oxide cathode material and preparation method thereof |
| CN105161705B (en) * | 2015-06-29 | 2018-06-05 | 山东玉皇新能源科技有限公司 | A kind of lithium manganese phosphate cladding nickel-cobalt lithium manganate cathode material and preparation method thereof |
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| CN105355880B (en) * | 2015-11-13 | 2018-06-08 | 山东精工电子科技有限公司 | A kind of LiFePO4/ C is modified the preparation method of tertiary cathode material |
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| CN109860582A (en) * | 2018-12-28 | 2019-06-07 | 蜂巢能源科技有限公司 | Positive electrode of lithium ion battery and preparation method thereof |
| CN109860582B (en) * | 2018-12-28 | 2022-04-19 | 蜂巢能源科技股份有限公司 | Positive electrode material of lithium ion battery and preparation method thereof |
| CN109904424A (en) * | 2019-02-28 | 2019-06-18 | 河南大学 | The method of one-step method surface cladding and the double modification LNMO positive electrodes of grade doping integration |
| WO2021037267A1 (en) * | 2019-08-29 | 2021-03-04 | 孚能科技(赣州)股份有限公司 | Core-shell structure lithium-ion battery positive electrode material, preparation method thereof, positive electrode plate, lithium-ion battery and application thereof |
| WO2023151334A1 (en) * | 2022-02-10 | 2023-08-17 | 中国第一汽车股份有限公司 | High-energy-density positive electrode material, positive electrode sheet and lithium-ion battery |
| CN116404167A (en) * | 2023-06-08 | 2023-07-07 | 江门市科恒实业股份有限公司 | Preparation method of surface-coated high-voltage lithium cobaltate |
| CN116404167B (en) * | 2023-06-08 | 2023-08-11 | 江门市科恒实业股份有限公司 | Preparation method of surface-coated high-voltage lithium cobaltate |
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