CN109950483B - Modified lithium cobalt phosphate cathode material for lithium ion battery and preparation method thereof - Google Patents
Modified lithium cobalt phosphate cathode material for lithium ion battery and preparation method thereof Download PDFInfo
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- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical class [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 title claims abstract description 57
- 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 20
- 239000010406 cathode material Substances 0.000 title claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920000123 polythiophene Polymers 0.000 claims abstract description 25
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011572 manganese Substances 0.000 claims abstract description 18
- 239000010452 phosphate Substances 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 16
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 16
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 16
- 229960004853 betadex Drugs 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 11
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 239000006228 supernatant Substances 0.000 claims abstract description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 28
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 14
- 108010077895 Sarcosine Proteins 0.000 claims description 14
- 229940043230 sarcosine Drugs 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- -1 phosphate compound Chemical class 0.000 claims description 6
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 5
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000000877 morphologic effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910000668 LiMnPO4 Inorganic materials 0.000 description 1
- SVXNDORSYNJGMW-UHFFFAOYSA-I P(=O)([O-])([O-])[O-].[Co](F)F.[Li+].[Li+].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Co](F)F.[Li+].[Li+].[Li+] SVXNDORSYNJGMW-UHFFFAOYSA-I 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- LEBWEOUIKVQVNY-UHFFFAOYSA-L lithium cobalt(2+) fluoro-dioxido-oxo-lambda5-phosphane Chemical compound [Li+].[Co+2].[O-]P([O-])(F)=O LEBWEOUIKVQVNY-UHFFFAOYSA-L 0.000 description 1
- 229940006116 lithium hydroxide Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 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 modified lithium cobalt phosphate anode material for a lithium ion battery and a preparation method thereof, wherein the anode material is polythiophene and nickel-manganese doped lithium cobalt phosphate with a nano carbon surface modified, and is prepared by the following steps: s1: dissolving a lithium source, a cobalt source, a nickel source and a manganese source in deionized water, adjusting the pH value to 5.5-6.0, adding a phosphate source and a structure directing agent after ultrasonic dispersion, carrying out hydrothermal reaction at the temperature of 200 ℃ for 6-10h, cooling and drying to obtain a precursor; s2: sintering; s3: dispersing polythiophene and beta-cyclodextrin in 50% ethanol solution, adding nickel-manganese doped lithium cobalt phosphate, ball milling for 1h, performing hydrothermal reaction at 180 ℃ for 6-10h, centrifuging, discarding supernatant, and drying to obtain the finished product. The method is simple and easy to control, and the prepared modified lithium cobalt phosphate has uniform morphological characteristics, regular crystal lattice, high discharge capacity, good cycle performance, high structural stability and high adhesion strength of the conductive film and is not easy to fall off.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a modified lithium cobalt phosphate cathode material for a lithium ion battery and a preparation method thereof.
Background
Lithium cobalt phosphate (LiCoPO)4) The special olivine structure enables the lithium ion battery to show the characteristics of excellent cycling stability, safety performance, high specific heat capacity and the like, and the lithium ion battery is a preferred anode material of a lithium ion battery of a new energy electric vehicle, the theoretical discharge specific capacity of the lithium ion battery is 167mAh/g, and the electrode potential of the lithium ion battery relative to lithium is 4.8V. At present, the preparation and application of lithium cobalt phosphate have become a research hotspot of lithium battery electrode materials, for example, patent with application number CN201510418652.1 discloses a lithium cobalt fluoride phosphate coated with silicon dioxide and a preparation method thereof; for example, patent with application number CN201510973998.8 discloses a graphene composite carbon-coated lithium cobalt phosphate material, and a preparation method and application thereof; for example, patent with application number CN201310309503.2 discloses a method for synthesizing a lithium cobalt phosphate as a positive electrode material for a lithium ion battery; for example, patent No. CN201410536799.6 discloses a hydrothermal preparation method of lithium cobalt fluorophosphate as a positive electrode material of a lithium secondary battery.
Lithium cobalt phosphate (LiCoPO)4) The polyanion groups exist in large quantity, so that a lithium ion transmission channel between adjacent layers is greatly compressed, the migration of lithium ions is further inhibited, and the conductivity is only about 10-9S/cm (25 ℃), much lower than LiCoO2、LiMn2O4For increasing the content of lithium cobalt phosphateThe preparation method has the advantages that the nano nickel oxide and the nano manganese oxide are doped in the preparation process of the lithium cobalt phosphate, and the polythiophene and the nano carbon are utilized for surface coating, so that the migration rate of lithium ions is improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a modified lithium cobalt phosphate cathode material for a lithium ion battery and a preparation method thereof.
The technical scheme of the invention is summarized as follows:
a modified lithium cobalt phosphate anode material for a lithium ion battery is prepared by modifying the surface of polythiophene and nanocarbon to form nickel-manganese doped lithium cobalt phosphate.
A preparation method of a modified lithium cobalt phosphate cathode material for a lithium ion battery comprises the following steps:
s1: dissolving a lithium source, a cobalt source, a nickel source and a manganese source in deionized water, adjusting the pH value to 5.5-6.0, adding a phosphate source and a structure directing agent N-acyl sarcosine sodium after ultrasonic dispersion, carrying out hydrothermal reaction for 6-10h at the temperature of 200 ℃, cooling and drying to obtain a precursor; 0.15-0.2mol of lithium source, 0.15-0.2mol of cobalt source, 0.005-0.01mol of nickel source, 0.01-0.02mol of manganese source, 0.2-0.3mol of phosphate source and 0.1-0.4mol of N-acyl sarcosine sodium per 1L of deionized water;
s2: presintering the precursor for 1h at the temperature of 200-;
s3: dispersing polythiophene and beta-cyclodextrin in 50% ethanol solution, adding nickel-manganese doped lithium cobalt phosphate, ball milling for 1h, performing hydrothermal reaction at 180 ℃ for 6-10h, centrifuging, discarding supernatant, and drying to obtain a finished product; the mass ratio of the polythiophene to the beta-cyclodextrin to the 50% ethanol solution to the nickel-manganese doped lithium cobalt phosphate is (0.01-0.1): (0.05-0.2): (5-7): 1.
preferably, the lithium source is a soluble lithium-based compound, specifically one of lithium nitrate, lithium sulfate, lithium chloride, lithium acetate, lithium carbonate, and lithium hydroxide.
Preferably, the cobalt source is a soluble cobalt salt, specifically one of cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetate.
Preferably, the nickel source is a soluble nickel salt, specifically one of nickel nitrate and nickel acetate.
Preferably, the manganese source is a soluble manganese-based compound, specifically one of potassium permanganate, potassium manganate, manganese nitrate and manganese acetate.
Preferably, the phosphate source is one of phosphoric acid or a soluble phosphate compound, wherein the soluble phosphate compound includes monopotassium phosphate, dipotassium phosphate, monoammonium phosphate, diammonium phosphate.
The invention has the beneficial effects that:
(1) the invention utilizes a hydrothermal method to prepare modified lithium cobalt phosphate, a nickel source and a manganese source are introduced in the preparation process, and because the radius and the energy level of a transition element Ni are similar to those of Co, part of Co element is replaced, and the modified lithium cobalt phosphate is prepared in LiCoPO4Lattice defects are formed inside, the conductivity and specific capacity of the electrode material are improved, and Mn element and Li are doped+、PO4 3-Reaction to produce LiMn2O4、LiMnPO4And LiCo(1-X)MnXPO4(X is more than 0 and less than 0.1), thereby improving the conductivity and the cycling stability of the electrode material, and finally, the conductive polymer polythiophene and the beta-cyclodextrin are used for preparing LiCoPO4The surface of the material reacts to generate a compact three-dimensional reticular polythiophene/nano carbon composite conductive film in situ, so that the migration rate of lithium ions is further improved.
(2) The method is simple and easy to control, and the prepared modified lithium cobalt phosphate has uniform morphological characteristics, regular crystal lattice, high discharge capacity, good cycle performance, high structural stability and high adhesion strength of the conductive film and is not easy to fall off.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
The invention provides a modified lithium cobalt phosphate anode material for a lithium ion battery and a preparation method thereof, wherein the anode material is polythiophene and nickel-manganese doped lithium cobalt phosphate with a nano carbon surface modified, and the preparation method comprises the following steps:
s1: dissolving a lithium source, a cobalt source, a nickel source and a manganese source in deionized water, adjusting the pH value to 5.5-6.0, adding a phosphate source and a structure directing agent N-acyl sarcosine sodium after ultrasonic dispersion, carrying out hydrothermal reaction for 6-10h at the temperature of 200 ℃, cooling and drying to obtain a precursor; 0.15-0.2mol of lithium source, 0.15-0.2mol of cobalt source, 0.005-0.01mol of nickel source, 0.01-0.02mol of manganese source, 0.2-0.3mol of phosphate source and 0.1-0.4mol of N-acyl sarcosine sodium per 1L of deionized water;
the lithium source is a soluble lithium-based compound, and specifically is one of lithium nitrate, lithium sulfate, lithium chloride, lithium acetate, lithium carbonate and lithium hydroxide; the cobalt source is soluble cobalt salt, specifically one of cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetate; the nickel source is soluble nickel salt, specifically one of nickel nitrate and nickel acetate; the manganese source is a soluble manganese-based compound, and is specifically one of potassium permanganate, potassium manganate, manganese nitrate and manganese acetate; the phosphate source is one of phosphoric acid or a soluble phosphate compound, wherein the soluble phosphate compound comprises monopotassium phosphate, dipotassium hydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate;
s2: presintering the precursor for 1h at the temperature of 200-;
s3: dispersing polythiophene and beta-cyclodextrin in 50% ethanol solution, adding nickel-manganese doped lithium cobalt phosphate, ball milling for 1h, performing hydrothermal reaction at 180 ℃ for 6-10h, centrifuging, discarding supernatant, and drying to obtain a finished product; the mass ratio of the polythiophene to the beta-cyclodextrin to the 50% ethanol solution to the nickel-manganese doped lithium cobalt phosphate is (0.01-0.1): (0.05-0.2): (5-7): 1.
example 1
A modified lithium cobalt phosphate anode material for a lithium ion battery is nickel-manganese doped lithium cobalt phosphate which is surface-modified by polythiophene and nanocarbon, and the preparation method comprises the following steps:
s1: dissolving lithium nitrate, cobalt nitrate, nickel nitrate and potassium permanganate in deionized water, adjusting the pH value to 5.5, performing ultrasonic dispersion, adding phosphoric acid and a structure directing agent N-acyl sarcosine sodium, performing hydrothermal reaction for 6 hours at 150 ℃, cooling and drying to obtain a precursor; every 1L of deionized water contains 0.15mol of lithium nitrate, 0.15mol of cobalt nitrate, 0.005mol of nickel nitrate, 0.01mol of potassium permanganate, 0.2mol of phosphoric acid and 0.1mol of N-acyl sarcosine sodium;
s2: presintering the precursor for 1h at 200 ℃ in a nitrogen environment, heating to 450 ℃ at the speed of 5 ℃/min, and sintering at constant temperature for 3h to obtain nickel-manganese doped lithium cobalt phosphate;
s3: dispersing polythiophene and beta-cyclodextrin in 50% ethanol solution, adding nickel-manganese doped lithium cobalt phosphate, ball milling for 1h, performing hydrothermal reaction at 120 ℃ for 6h, centrifuging, removing supernatant, and drying to obtain a finished product; the mass ratio of the polythiophene to the beta-cyclodextrin to the 50% ethanol solution to the nickel-manganese doped lithium cobalt phosphate is 0.01: 0.05: 5: 1.
example 2
A modified lithium cobalt phosphate anode material for a lithium ion battery is nickel-manganese doped lithium cobalt phosphate which is surface-modified by polythiophene and nanocarbon, and the preparation method comprises the following steps:
s1: dissolving lithium sulfate, cobalt sulfate, nickel nitrate and potassium manganate in deionized water, adjusting the pH value to 5.8, performing ultrasonic dispersion, adding potassium dihydrogen phosphate and a structure directing agent N-acyl sarcosine sodium, performing hydrothermal reaction at 180 ℃ for 8 hours, cooling and drying to obtain a precursor; every 1L of deionized water, 0.18mol of lithium sulfate, 0.18mol of cobalt sulfate, 0.0075mol of nickel nitrate, 0.015mol of potassium manganate, 0.25mol of monopotassium phosphate and 0.25mol of N-acyl sarcosine sodium;
s2: presintering the precursor for 1h at 250 ℃ in a nitrogen environment, heating to 530 ℃ at the speed of 7.5 ℃/min, and sintering at constant temperature for 6h to obtain nickel-manganese doped lithium cobalt phosphate;
s3: dispersing polythiophene and beta-cyclodextrin in 50% ethanol solution, adding nickel-manganese doped lithium cobalt phosphate, ball milling for 1h, performing hydrothermal reaction for 8h at 150 ℃, centrifuging, discarding supernatant, and drying to obtain a finished product; the mass ratio of the polythiophene to the beta-cyclodextrin to the 50% ethanol solution to the nickel-manganese doped lithium cobalt phosphate is 0.05: 0.12: 6: 1.
example 3
A modified lithium cobalt phosphate anode material for a lithium ion battery is nickel-manganese doped lithium cobalt phosphate which is surface-modified by polythiophene and nanocarbon, and the preparation method comprises the following steps:
s1: dissolving lithium hydroxide, cobalt acetate, nickel acetate and manganese nitrate in deionized water, adjusting the pH value to 6.0, performing ultrasonic dispersion, adding dipotassium hydrogen phosphate and a structure directing agent N-acyl sarcosine sodium, performing hydrothermal reaction for 10 hours at 200 ℃, cooling and drying to obtain a precursor; 0.2mol of lithium hydroxide, 0.2mol of cobalt acetate, 0.01mol of nickel acetate, 0.02mol of manganese nitrate, 0.3mol of dipotassium phosphate and 0.4mol of N-acyl sarcosine sodium per 1L of deionized water;
s2: presintering the precursor for 1h at 300 ℃ in a nitrogen environment, heating to 600 ℃ at the speed of 10 ℃/min, and sintering at constant temperature for 8h to obtain nickel-manganese doped lithium cobalt phosphate;
s3: dispersing polythiophene and beta-cyclodextrin in 50% ethanol solution, adding nickel-manganese doped lithium cobalt phosphate, ball milling for 1h, performing hydrothermal reaction at 180 ℃ for 10h, centrifuging, removing supernatant, and drying to obtain a finished product; the mass ratio of the polythiophene to the beta-cyclodextrin to the 50% ethanol solution to the nickel-manganese doped lithium cobalt phosphate is 0.1: 0.2: 7: 1.
example 4 the modified lithium cobalt phosphate cathode materials prepared in examples 1-3 were tested for electrochemical properties:
the modified lithium cobalt phosphate cathode materials prepared in examples 1 to 3 and a lithium metal sheet are assembled into a battery, the battery is tested in a voltage range of 3.0 to 5.2V and is charged and discharged at a rate of 0.5C, and the test results are shown in the following table:
| example 1 | Example 2 | Example 3 | |
| Specific capacity of first charge/mAh/g | 179.1 | 181.3 | 180.8 |
| Specific capacity of first discharge/mAh/g | 162.8 | 164.6 | 163.2 |
| First cycle coulombic efficiency/%) | 90.9 | 90.8 | 90.3 |
| Average specific discharge capacity/mAh/g | 145.3 | 146.1 | 145.8 |
| Charge constant current ratio/%) | 98.1 | 97.7 | 98.3 |
| conductivity/S/cm | 4.6×10-4 | 5.1×10-4 | 4.5×10-4 |
The invention obviously improves the conductivity of the lithium cobalt phosphate material and improves the electrochemical performance of the lithium cobalt phosphate material.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (7)
1. A modified lithium cobalt phosphate anode material for a lithium ion battery is characterized in that the anode material is polythiophene and nickel-manganese doped lithium cobalt phosphate with a nano carbon surface modified; the preparation method of the modified lithium cobalt phosphate cathode material for the lithium ion battery comprises the following steps:
s1: dissolving a lithium source, a cobalt source, a nickel source and a manganese source in deionized water, adjusting the pH value to 5.5-6.0, adding a phosphate source and a structure directing agent N-acyl sarcosine sodium after ultrasonic dispersion, carrying out hydrothermal reaction for 6-10h at the temperature of 200 ℃, cooling and drying to obtain a precursor; 0.15-0.2mol of lithium source, 0.15-0.2mol of cobalt source, 0.005-0.01mol of nickel source, 0.01-0.02mol of manganese source, 0.2-0.3mol of phosphate source and 0.1-0.4mol of N-acyl sarcosine sodium per 1L of deionized water;
s2: presintering the precursor for 1h at the temperature of 200-;
s3: dispersing polythiophene and beta-cyclodextrin in 50% ethanol solution, adding nickel-manganese doped lithium cobalt phosphate, ball milling for 1h, performing hydrothermal reaction at 180 ℃ for 6-10h, centrifuging, discarding supernatant, and drying to obtain a finished product; the mass ratio of the polythiophene to the beta-cyclodextrin to the 50% ethanol solution to the nickel-manganese doped lithium cobalt phosphate is (0.01-0.1): (0.05-0.2): (5-7): 1.
2. a preparation method of a modified lithium cobalt phosphate cathode material for a lithium ion battery is characterized by comprising the following steps:
s1: dissolving a lithium source, a cobalt source, a nickel source and a manganese source in deionized water, adjusting the pH value to 5.5-6.0, adding a phosphate source and a structure directing agent N-acyl sarcosine sodium after ultrasonic dispersion, carrying out hydrothermal reaction for 6-10h at the temperature of 200 ℃, cooling and drying to obtain a precursor; 0.15-0.2mol of lithium source, 0.15-0.2mol of cobalt source, 0.005-0.01mol of nickel source, 0.01-0.02mol of manganese source, 0.2-0.3mol of phosphate source and 0.1-0.4mol of N-acyl sarcosine sodium per 1L of deionized water;
s2: presintering the precursor for 1h at the temperature of 200-;
s3: dispersing polythiophene and beta-cyclodextrin in 50% ethanol solution, adding nickel-manganese doped lithium cobalt phosphate, ball milling for 1h, performing hydrothermal reaction at 180 ℃ for 6-10h, centrifuging, discarding supernatant, and drying to obtain a finished product; the mass ratio of the polythiophene to the beta-cyclodextrin to the 50% ethanol solution to the nickel-manganese doped lithium cobalt phosphate is (0.01-0.1): (0.05-0.2): (5-7): 1.
3. the method according to claim 2, wherein the lithium source is a soluble lithium-based compound, specifically one of lithium nitrate, lithium sulfate, lithium chloride, lithium acetate, lithium carbonate, and lithium hydroxide.
4. The method for preparing the modified lithium cobalt phosphate cathode material for the lithium ion battery according to claim 2, wherein the cobalt source is soluble cobalt salt, specifically one of cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetate.
5. The method for preparing the modified lithium cobalt phosphate cathode material for the lithium ion battery according to claim 2, wherein the nickel source is soluble nickel salt, specifically one of nickel nitrate and nickel acetate.
6. The method for preparing the modified lithium cobalt phosphate positive electrode material for the lithium ion battery according to claim 2, wherein the manganese source is a soluble manganese-based compound, specifically one of potassium permanganate, potassium manganate, manganese nitrate and manganese acetate.
7. The method for preparing the modified lithium cobalt phosphate cathode material for the lithium ion battery according to claim 2, wherein the phosphate source is one of phosphoric acid or a soluble phosphate compound, wherein the soluble phosphate compound comprises potassium dihydrogen phosphate, dipotassium hydrogen phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
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