CN104393282A - Preparation method of multi-element cathode material coated by graphene - Google Patents
Preparation method of multi-element cathode material coated by graphene Download PDFInfo
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- CN104393282A CN104393282A CN201410793069.4A CN201410793069A CN104393282A CN 104393282 A CN104393282 A CN 104393282A CN 201410793069 A CN201410793069 A CN 201410793069A CN 104393282 A CN104393282 A CN 104393282A
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- nickel
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000010406 cathode material Substances 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000011149 active material Substances 0.000 claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 17
- 239000004411 aluminium Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 12
- WUGCBSIBTVUHPE-UHFFFAOYSA-J [Co++].[Ni++].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O Chemical compound [Co++].[Ni++].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O WUGCBSIBTVUHPE-UHFFFAOYSA-J 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- -1 aminopyridine derivative of graphene Chemical class 0.000 claims description 8
- 150000003927 aminopyridines Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 150000005005 aminopyrimidines Chemical class 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical class O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 229910014063 LiNi1-xCoxO2 Inorganic materials 0.000 abstract 1
- 229910014402 LiNi1—xCoxO2 Inorganic materials 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of multi-element cathode material coated by graphene. The active material of the multi-element cathode material comprises an inner layer and an outer layer, wherein the active material has the following chemical formula (1-a) LiNi1-xCoxO2.aLiMn0.3Al0.7O2, wherein a is equal to 0.3-0.35, and the x is equal to 0.25-0.45. The method comprises the following steps: (1) preparing the active material; (2) preparing graphene derivate materials; (3) coating the active material by the graphene derivate materials. The multi-element cathode material prepared by the method disclosed by the invention adopts a two-layer structures with various component matching ratios, the proportion of the nickel in the inner layer is the highest, so that the high capacity of the material is ensured; the outer layer has higher cobalt content, so that the cycling stability of the material is ensured; finally, another layer of graphene derivate material is adopted for coating the active material, so that the activity and the capacity of the material are further improved. Therefore, when the cathode materials are applied to lithium batteries, the specific capacity is higher, and the stability is good.
Description
Technical field
The present invention relates to a kind of preparation method of polynary positive pole material of graphene coated.
Background technology
Along with the development of various new forms of energy, various electronic equipment, as portable electric appts and electric automobile etc., more extensive to the demand of large-capacity high-power chemical power source.
Business-like positive electrode mainly contains cobalt acid lithium (LiCoO at present
2), lithium nickelate (LiNiO
2), LiMn2O4 (LiMnO
2) and nickel-cobalt-manganese ternary material.Stratiform lithium cobaltate cathode material is business-like lithium ion battery the earliest, although its energy density is high, its cost is high, and environmental pollution is also larger; Spinel lithium manganese oxide anode material cost is low, and fail safe is high, but its specific capacity is low and high-temperature behavior is poor; Stratiform lithium nickelate positive electrode capacity is high, but synthesis condition is harsh; Olivine lithium iron phosphate cathode material is moderate, and cycle performance is very good, but cryogenic property is bad, and volumetric specific energy is lower.Make a general survey of several positive electrodes main at present, the advantage that polynary positive pole material display is unique, assemble the advantage of cobalt acid lithium, LiMn2O4 and lithium nickelate three kinds of positive electrodes, i.e. high-energy, high power capacity, high securities etc., charge and discharge platform and cobalt acid lithium is close, is considered to most possible substituting cobalt acid lithium and one of business-like positive electrode.But the cycle performance of this material is general, have impact on the commercial applications of this material.
Summary of the invention
The invention provides a kind of preparation method of polynary positive pole material of graphene coated, the positive electrode using the method to prepare, has higher energy density and good cyclical stability.
To achieve these goals, the invention provides a kind of preparation method of polynary positive pole material of graphene coated, the active material of this polynary positive pole material comprises internal layer and skin, and wherein this active material possesses following chemical formula (1-a) LiNi
1-xco
xo
2. aLiMn
0.3al
0.7o
2, wherein a=0.3-0.35, x=0.25-0.45, the method comprises the steps:
(1) active material is prepared
Compound concentration is the acetic acid solution of 1-1.5mol/L, nickelous sulfate, cobaltous sulfate are configured to according to being dissolved in deionized water after mol ratio 1-x:x mixing the mixed nitrate solution that metal ion total concentration is 3-4mol/L, above-mentioned acetic acid solution is placed in the reactor that band stirs, strong agitation, mixing salt solution is instilled in reactor, in regulating and controlling reactor reactant liquor temperature and remain on 55-60 DEG C, after having fed in raw material, continue to stir ageing, wherein the amount of acetic acid solution should enough make all nickel and cobalt ions generate nickel acetate cobalt;
Separation of Solid and Liquid, spends the solid product of deionized water Separation of Solid and Liquid gained, and the product after washing is dry, obtains nickel acetate cobalt powder body, by nickel acetate cobalt powder body air atmosphere 500-550 DEG C calcining 4-6h, and obtained internal layer precursor, pulverize after cooling, for subsequent use;
The sal limonis of cobalt manganese aluminium is dissolved in deionized water, wherein the mol ratio of manganese aluminium element is 3:7, obtain the citrate solution that metal ion total concentration is 0.5-1mol/L, the precursor powder having an internal layer by above-mentioned and dispersant acetone are put into the citrate solution prepared in the lump and are mixed, the mol ratio of the manganese aluminium element total amount in the precursor powder of wherein internal layer in nickel cobalt element total amount and citrate solution is 1-a:a, stir and form suspension, then will obtain active material presoma after spray dried;
By after active material presoma and lithium carbonate mixing with the speed ball milling 4-5h of 300-350r/min, the mol ratio 1:1 of the lithium in the integral molar quantity of the nickel cobalt manganese aluminium wherein in precursor and lithium carbonate, then calcines 8-10h, obtains active material at 850-900 DEG C;
(2) Graphene derivative material is prepared
By graphite oxide dissolve in deionized water, then under agitation add the ethanolic solution of aminopyrimidine, then at the temperature of 70-75 DEG C back flow reaction 30-40h, obtain the aminopyridine derivative of graphene oxide;
The back flow reaction 10-15h at the temperature of 85-90 DEG C by described aminopyridine derivative and enough hydrazine hydrates, obtain the aminopyridine derivative of Graphene, by the aminopyridine derivative of described Graphene at 100-120 DEG C of annealing 5-8h, obtain Graphene derivative material;
(3) the coated active material of Graphene derivative
Above-mentioned active material and the above-mentioned Graphene derivative material ratio by weight 100: 3-4 is mixed, by compound in planetary ball mill with rotating speed 400-450r/min ball milling 3-5h, after the material drying after ball milling, sintering is heat-treated in High Purity Nitrogen air-flow, with 5-10 DEG C/min ramp, at temperature 750-800 DEG C of Isothermal sinter 10-15h, lower the temperature with 10-15 DEG C/min, obtain final products.
Polynary positive pole material prepared by the present invention, there is the two-layer Rotating fields that component proportion is different, wherein internal layer nickel proportion is the highest, to ensure the high power capacity of material, skin has higher cobalt content, to ensure the cyclical stability of material, finally cover activity and capacity that one deck Graphene derivative material improves material further again.Therefore this positive electrode is when for lithium ion battery, has higher specific capacity and good stability.
Embodiment
embodiment one
This active material of this embodiment possesses following chemical formula 0.7LiNi
0.75co
0.25o
2. 0.3LiMn
0.3al
0.7o
2.
Compound concentration is the acetic acid solution of 1mol/L, nickelous sulfate, cobaltous sulfate are configured to according to being dissolved in deionized water after mol ratio 0.75:0.25 mixing the mixed nitrate solution that metal ion total concentration is 3mol/L, above-mentioned acetic acid solution is placed in the reactor that band stirs, strong agitation, mixing salt solution is instilled in reactor, in regulating and controlling reactor reactant liquor temperature and remain on 55 DEG C, after having fed in raw material, continue to stir ageing, wherein the amount of acetic acid solution should enough make all nickel and cobalt ions generate nickel acetate cobalt; Separation of Solid and Liquid, spends the solid product of deionized water Separation of Solid and Liquid gained, and the product after washing is dry, obtains nickel acetate cobalt powder body, by nickel acetate cobalt powder body air atmosphere 500 DEG C calcining 6h, and obtained internal layer precursor, pulverize after cooling, for subsequent use.
The sal limonis of cobalt manganese aluminium is dissolved in deionized water, wherein the mol ratio of manganese aluminium element is 3:7, obtain the citrate solution that metal ion total concentration is 0.5mol/L, the precursor powder having an internal layer by above-mentioned and dispersant acetone are put into the citrate solution prepared in the lump and are mixed, the mol ratio of the manganese aluminium element total amount in the precursor powder of wherein internal layer in nickel cobalt element total amount and citrate solution is 0.7:0.3, stir and form suspension, then will obtain active material presoma after spray dried; By after active material presoma and lithium carbonate mixing with the speed ball milling 5h of 300r/min, the mol ratio 1:1 of the lithium in the integral molar quantity of the nickel cobalt manganese aluminium wherein in precursor and lithium carbonate, then calcines 10h, obtains active material at 850 DEG C.
Graphite oxide is dissolved in deionized water, then the ethanolic solution of aminopyrimidine is under agitation added, back flow reaction 40h at the temperature of 70 DEG C again, obtain the aminopyridine derivative of graphene oxide, the back flow reaction 15h at the temperature of 85 DEG C by described aminopyridine derivative and enough hydrazine hydrates, obtain the aminopyridine derivative of Graphene, by the aminopyridine derivative of described Graphene at 100 DEG C of annealing 8h, obtain Graphene derivative material.
Above-mentioned active material and the above-mentioned Graphene derivative material ratio by weight 100: 3 is mixed, by compound in planetary ball mill with rotating speed 400r/min ball milling 5h, after the material drying after ball milling, sintering is heat-treated in High Purity Nitrogen air-flow, with 5 DEG C/min ramp, at temperature 750 DEG C of Isothermal sinter 15h, lower the temperature with 10 DEG C/min, obtain final products.
embodiment two
This active material of this embodiment possesses following chemical formula 0.65LiNi
0.55co
0.45o
2. 0.35LiMn
0.3al
0.7o
2.
Compound concentration is the acetic acid solution of 1.5mol/L, nickelous sulfate, cobaltous sulfate are configured to according to being dissolved in deionized water after mol ratio 0.55:0.45 mixing the mixed nitrate solution that metal ion total concentration is 4mol/L, above-mentioned acetic acid solution is placed in the reactor that band stirs, strong agitation, mixing salt solution is instilled in reactor, in regulating and controlling reactor reactant liquor temperature and remain on 60 DEG C, after having fed in raw material, continue to stir ageing, wherein the amount of acetic acid solution should enough make all nickel and cobalt ions generate nickel acetate cobalt; Separation of Solid and Liquid, spends the solid product of deionized water Separation of Solid and Liquid gained, and the product after washing is dry, obtains nickel acetate cobalt powder body, by nickel acetate cobalt powder body air atmosphere 550 DEG C calcining 4h, and obtained internal layer precursor, pulverize after cooling, for subsequent use.
The sal limonis of cobalt manganese aluminium is dissolved in deionized water, wherein the mol ratio of manganese aluminium element is 3:7, obtain the citrate solution that metal ion total concentration is 1mol/L, the precursor powder having an internal layer by above-mentioned and dispersant acetone are put into the citrate solution prepared in the lump and are mixed, the mol ratio of the manganese aluminium element total amount in the precursor powder of wherein internal layer in nickel cobalt element total amount and citrate solution is 0.65:0.35, stir and form suspension, then will obtain active material presoma after spray dried; By after active material presoma and lithium carbonate mixing with the speed ball milling 4h of 350r/min, the mol ratio 1:1 of the lithium in the integral molar quantity of the nickel cobalt manganese aluminium wherein in precursor and lithium carbonate, then calcines 8h, obtains active material at 900 DEG C.
Graphite oxide is dissolved in deionized water, then the ethanolic solution of aminopyrimidine is under agitation added, back flow reaction 30h at the temperature of 75 DEG C again, obtain the aminopyridine derivative of graphene oxide, the back flow reaction 10h at the temperature of 90 DEG C by described aminopyridine derivative and enough hydrazine hydrates, obtain the aminopyridine derivative of Graphene, by the aminopyridine derivative of described Graphene at 120 DEG C of annealing 5h, obtain Graphene derivative material.
Above-mentioned active material and the above-mentioned Graphene derivative material ratio by weight 100: 4 is mixed, by compound in planetary ball mill with rotating speed 450r/min ball milling 3h, after the material drying after ball milling, sintering is heat-treated in High Purity Nitrogen air-flow, with 10 DEG C/min ramp, at temperature 800 DEG C of Isothermal sinter 10h, lower the temperature with 15 DEG C/min, obtain final products.
comparative example
Compound concentration is the nickel of 2M, cobalt and manganese salt solution, wherein, and nickel: cobalt: the molar ratio of manganese is 1: 1: 1.The above-mentioned salting liquid prepared is injected with the speed of 1L/h the reactor that rotating speed is 200rps, injects the NaOH solution of 6M simultaneously, note regulating aqueous slkali flow velocity, keep pH value between 10-11.After 27.5h, salting liquid is squeezed in reactor completely, and precursor power has reacted.By the solidliquid mixture after having reacted by centrifugation, wash and at 100 DEG C, dry 10h to neutrality.By presoma and the lithium carbonate after drying in molar ratio 1: 1.05 mix after in Muffle furnace 900 DEG C of roasting 10h, the material after roasting obtains homogeneous LiNi after fragmentation is sieved
1/3co
1/3mn
1/3o
2ternary material.
Take above-described embodiment one, two and the comparative example products therefrom of equal in quality, be assembled into the simulated battery of same dimensions respectively, negative pole is metal lithium sheet, and barrier film is celgard2400, and electrolyte is LiPF
6(EC:DEC:=1:1 :).At probe temperature is 45 DEG C, carry out electric performance test, after tested this embodiment one with two material compared with the product of comparative example, discharge capacity improves 25.5-31.7 mAh/g first, 100 times circulation after capability retention improve more than 10-15%.
Claims (1)
1. a preparation method for the polynary positive pole material of graphene coated, the active material of this polynary positive pole material comprises internal layer and skin, and wherein this active material possesses following chemical formula (1-a) LiNi
1-xco
xo
2. aLiMn
0.3al
0.7o
2, wherein a=0.3-0.35, x=0.25-0.45, the method comprises the steps:
(1) active material is prepared
Compound concentration is the acetic acid solution of 1-1.5mol/L, nickelous sulfate, cobaltous sulfate are configured to according to being dissolved in deionized water after mol ratio 1-x:x mixing the mixed nitrate solution that metal ion total concentration is 3-4mol/L, above-mentioned acetic acid solution is placed in the reactor that band stirs, strong agitation, mixing salt solution is instilled in reactor, in regulating and controlling reactor reactant liquor temperature and remain on 55-60 DEG C, after having fed in raw material, continue to stir ageing, wherein the amount of acetic acid solution should enough make all nickel and cobalt ions generate nickel acetate cobalt;
Separation of Solid and Liquid, spends the solid product of deionized water Separation of Solid and Liquid gained, and the product after washing is dry, obtains nickel acetate cobalt powder body, by nickel acetate cobalt powder body air atmosphere 500-550 DEG C calcining 4-6h, and obtained internal layer precursor, pulverize after cooling, for subsequent use;
The sal limonis of cobalt manganese aluminium is dissolved in deionized water, wherein the mol ratio of manganese aluminium element is 3:7, obtain the citrate solution that metal ion total concentration is 0.5-1mol/L, the precursor powder having an internal layer by above-mentioned and dispersant acetone are put into the citrate solution prepared in the lump and are mixed, the mol ratio of the manganese aluminium element total amount in the precursor powder of wherein internal layer in nickel cobalt element total amount and citrate solution is 1-a:a, stir and form suspension, then will obtain active material presoma after spray dried;
By after active material presoma and lithium carbonate mixing with the speed ball milling 4-5h of 300-350r/min, the mol ratio 1:1 of the lithium in the integral molar quantity of the nickel cobalt manganese aluminium wherein in precursor and lithium carbonate, then calcines 8-10h, obtains active material at 850-900 DEG C;
(2) Graphene derivative material is prepared
By graphite oxide dissolve in deionized water, then under agitation add the ethanolic solution of aminopyrimidine, then at the temperature of 70-75 DEG C back flow reaction 30-40h, obtain the aminopyridine derivative of graphene oxide;
The back flow reaction 10-15h at the temperature of 85-90 DEG C by described aminopyridine derivative and enough hydrazine hydrates, obtain the aminopyridine derivative of Graphene, by the aminopyridine derivative of described Graphene at 100-120 DEG C of annealing 5-8h, obtain Graphene derivative material;
(3) the coated active material of Graphene derivative
Above-mentioned active material and the above-mentioned Graphene derivative material ratio by weight 100: 3-4 is mixed, by compound in planetary ball mill with rotating speed 400-450r/min ball milling 3-5h, after the material drying after ball milling, sintering is heat-treated in High Purity Nitrogen air-flow, with 5-10 DEG C/min ramp, at temperature 750-800 DEG C of Isothermal sinter 10-15h, lower the temperature with 10-15 DEG C/min, obtain final products.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106784654A (en) * | 2016-11-28 | 2017-05-31 | 荆门市格林美新材料有限公司 | A kind of preparation method of graphene coated cobalt acid lithium material |
| CN108539131A (en) * | 2018-03-27 | 2018-09-14 | 宁夏汉尧石墨烯储能材料科技有限公司 | A kind of graphene is modified the preparation method of nickelic system's positive electrode |
| CN111492526A (en) * | 2018-11-29 | 2020-08-04 | 株式会社Lg化学 | Electrode assembly |
| CN113716549A (en) * | 2020-12-16 | 2021-11-30 | 山东海科创新研究院有限公司 | Multi-element coated core-shell structure lithium ion positive electrode material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106784654A (en) * | 2016-11-28 | 2017-05-31 | 荆门市格林美新材料有限公司 | A kind of preparation method of graphene coated cobalt acid lithium material |
| CN108539131A (en) * | 2018-03-27 | 2018-09-14 | 宁夏汉尧石墨烯储能材料科技有限公司 | A kind of graphene is modified the preparation method of nickelic system's positive electrode |
| CN111492526A (en) * | 2018-11-29 | 2020-08-04 | 株式会社Lg化学 | Electrode assembly |
| CN111492526B (en) * | 2018-11-29 | 2023-07-25 | 株式会社Lg新能源 | Electrode assembly, secondary battery, and secondary battery module |
| US11909040B2 (en) | 2018-11-29 | 2024-02-20 | Lg Energy Solution, Ltd. | Electrode assembly |
| CN113716549A (en) * | 2020-12-16 | 2021-11-30 | 山东海科创新研究院有限公司 | Multi-element coated core-shell structure lithium ion positive electrode material and preparation method thereof |
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