CN103887508A - Preparation method of polyelectrolyte-coated LiNi0.5Mn1.5O4 positive electrode material - Google Patents
Preparation method of polyelectrolyte-coated LiNi0.5Mn1.5O4 positive electrode material Download PDFInfo
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- CN103887508A CN103887508A CN201410109284.8A CN201410109284A CN103887508A CN 103887508 A CN103887508 A CN 103887508A CN 201410109284 A CN201410109284 A CN 201410109284A CN 103887508 A CN103887508 A CN 103887508A
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- polyelectrolyte
- lithium
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- 229920000867 polyelectrolyte Polymers 0.000 title claims abstract description 34
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 title abstract 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 26
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910013716 LiNi Inorganic materials 0.000 claims description 25
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002152 aqueous-organic solution Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 claims description 2
- 238000005373 pervaporation Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- UGPIGYYLADCIFW-UHFFFAOYSA-N dioxido(dioxo)manganese;nickel(2+) Chemical compound [Ni+2].[O-][Mn]([O-])(=O)=O UGPIGYYLADCIFW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a preparation method of a polyelectrolyte-coated LiNi0.5Mn1.5O4 positive electrode material. The preparation method comprises the following steps: coating LiNi0.5Mn1.5O4 with a polyelectrolyte solution, and drying to obtain polyelectrolyte-coated LiNi0.5Mn1.5O4, wherein the polyelectrolyte is one or a mixture of several of lithium polyacrylate, lithium polymethylacrylate, lithium polymaleate, lithium poly(methyl vinyl ether maleic acid copolymer) and lithium polyfumarate. According to the coating method, a layer of polyelectrolyte membrane is formed on the surface of LiNi0.5Mn1.5O4, so that the compatibility with an electrolyte solution is improved. Therefore, the polyelectrolyte-coated LiNi0.5Mn1.5O4 positive electrode material has the characteristics of high specific capacity, high rate and long cycle life.
Description
Technical field
The present invention relates to a kind of preparation method of high-voltage anode material of lithium ion batteries, particularly relate to the preparation method of surperficial coating spinelle type high voltage nickel manganate cathode material for lithium, belong to anode material for lithium-ion batteries technical field.
Background technology
Charging/discharging voltage platform is greater than the positive electrode of 4.5 V, is commonly referred to as high-voltage anode material.For example, LiNi
0.5mn
1.5o
4, working voltage platform is 4.7 V, is typical 5 V high-voltage anode materials.LiNi
0.5mn
1.5o
4there is three-dimensional lithium ion passage, the Ni of 0.5mol
2+replace and make 1mol LiMn
2o
4middle Mn
3+all become Mn
4+(LiNi
0.5mn
1.5o
4) and do not affect the theoretical specific capacity of material.Meanwhile, due to LiNi
0.5mn
1.5o
4in there is not Mn
3+, do not have Jahn-Teller effect to produce structural aberration, cycle performance, high-temperature behavior are all significantly improved.
It is generally acknowledged that high potential electrolyte problem of resistance is the key issue in the large-scale production of nickel LiMn2O4 and application.Surface is coated can improve LiNi
0.5mn
1.5o
4with the compatibility of electrolyte, improve its chemical property, many researchers have carried out the work of this respect.For example: the AlF of CN102324512A
3surface is coated, and CN102983324A aluminium zinc oxide AZO surface is coated, the solid electrolyte Li of the coated and CN102683709A in the cupric oxide surface of CN103337621A
5la
3m
2o
12(M=Ta, Nb) surface is coated.Above-mentioned surface coating method all will pass through, the mixing of electrode material and coated presoma, dry, and then 500 ℃ of calcinings of high temperature obtain inorganic compound coating layers.Method technique is loaded down with trivial details needs again high-temperature calcination.
Summary of the invention
Deficiency for above-mentioned conventional surface method for coating of the present invention, proposes a kind of simple, quick polyelectrolyte coated LiNi in surface
0.5mn
1.5o
4the method of positive electrode, the coated LiNi in PAALi surface prepared by the method
0.5mn
1.5o
4positive electrode has high working voltage platform, height ratio capacity, high magnification, long-life feature.
Technical scheme of the present invention is: a kind of polyelectrolyte is coated LiNi
0.5mn
1.5o
4the preparation method of positive electrode, the coated LiNi of application polyelectrolyte solution
0.5mn
1.5o
4, the then dry coated LiNi of polyelectrolyte that obtains
0.5mn
1.5o
4, described polyelectrolyte is the mixture of a kind of or above several materials in Lithium polyacrylate, polymethylacrylic acid lithium, poly lithium, poly-(methyl vinyl ether copolymerization maleic acid) lithium or poly-fumaric acid lithium.
Further, described polyelectrolyte solution is the polyelectrolyte aqueous solution or organic solution.
Further, the aqueous solution that described polyelectrolyte solution is Lithium polyacrylate.
Further, described Lithium polyacrylate is reacted and is obtained or adopt Lithium acrylate polymerization to obtain by polymer chemistry.
Further, specifically comprise the following steps:
(1) taking mean molecule quantity is 1000 ~ 4000000 polyacrylic acid, configuration LiOHH
2the O aqueous solution, dropwise joins LiOH solution in polyacrylic acid, until the pH value of solution is 8, above-mentioned gained solution is obtained to solid matter Lithium polyacrylate through pervaporation, after dry;
(2) take Lithium polyacrylate and LiNi
0.5mn
1.5o
4powder, the mixing that is dissolved in water, vacuumize, obtains the coated LiNi in Lithium polyacrylate surface
0.5mn
1.5o
4positive electrode.
Further, specifically comprise the following steps:
(1) take mean molecule quantity be 3000 polyacrylic acid in container, take LiOHH
2o is dissolved in distilled water and obtains LiOH solution, LiOH solution is dropwise joined in polyacrylic acid, until the pH value of solution is 8,80 ℃ of heating of gained solution are steamed to thick, then move to vacuum drying chamber in 100 ℃ of vacuumize 24 h, obtain white solid matter Lithium polyacrylate;
(2) take according to a certain percentage Lithium polyacrylate and the LiNi of certain mass
0.5mn
1.5o
4powder, adds distilled water to carry out fully dissolving and mixing, and moves to vacuumize vacuumize 24 h at 100 ℃ on electric jacket after tentatively evaporating, and obtains the coated LiNi in Lithium polyacrylate surface
0.5mn
1.5o
4positive electrode.
Further, the coated part by weight of Lithium polyacrylate is 0.25～10%.Preferably, the coated part by weight of Lithium polyacrylate is 0.25～5%.
Polyelectrolyte comprises Lithium polyacrylate, polymethylacrylic acid lithium, poly lithium, poly-(methyl vinyl ether copolymerization maleic acid) lithium, poly-fumaric acid lithium, or the mixture of above several materials.All contain on the side chain of above polymer-COOLi group, polymer and LiOH, Li that can be contained by side chain-COOH group
2cO
3or both mixtures react acquisition by polymer chemistry; Also can the polymerization of be contained by side chain-COOLi group vinyl monomer obtain.Typical such polyelectrolyte is Lithium polyacrylate (PAALi), and because PAALi self-conductance rate is low, its application study for lithium ion polymer electrolyte is also less.But PAALi, is coated on electrode material, can be swelling under electrolyte effect, form one deck and be coated on the polymer film on electrode material.This film has very high lithium ion conduction ability, and meanwhile, PAALi decomposition electric potential is far above general electrolyte (LiPF
6, LiBOB etc.), the combination of two aspects can obviously improve LiNi
0.5mn
1.5o
4the chemical property of positive electrode.
The present invention compared with prior art tool has the following advantages:
1, the present invention by method for coating at LiNi
0.5mn
1.5o
4surface has formed one deck polyelectrolyte film, has strengthened and the compatibility of electrolyte, therefore has the feature of height ratio capacity, high magnification, long circulation life.
2, patent of the present invention, for the drawback of method for coating above, proposes polyelectrolyte surface and is coated to improve LiNi
0.5mn
1.5o
4chemical property.This method for coating only needs low temperature drying, does not need high-temperature calcination, has simply, feature fast.
Accompanying drawing explanation
Fig. 1 is embodiment 1 and the charging and discharging curve comparison of comparative example 1 under 0.5 C.
Fig. 2 is embodiment 1 and the cycle performance curve of comparative example 1 under different multiplying.
Fig. 3 is embodiment 1 and the cycle performance curve of comparative example 1 under 1 C multiplying power.
Embodiment
Take mean molecule quantity and be in 3000 polyacrylic acid 10.2g to 200ml evaporating dish, take LiOHH
2o 2.32g, be dissolved in 36g distilled water and obtain LiOH solution, LiOH solution is dropwise joined in evaporating dish, until the pH value of solution is 8, above-mentioned gained solution is tentatively extremely thick in 80 ℃ of steamings of electric jacket, then mixture is moved to vacuum drying chamber in 100 ℃ of vacuumize 24 h, obtain white solid matter PAALi.Take LiNi
0.5mn
1.5o
4finished product 4.975 g, PAALi 0.025 g, in this mixture, PAALi mass fraction is 0.5%.By the LiNi taking
0.5mn
1.5o
4, PAALi 0.025g fully dissolves and is mixed in 5mL water, carries out tentatively moving to vacuum drying chamber in 100 ℃ of vacuumize 24h after stirring evaporation on electric jacket, obtains 5g LNM 0.5%PAALi powder sample.
Take Super P 0.1 g, LNM@0.5%PAALi0.8 g, solid content 3 wt.% aqueous adhesive LA132(Chengdu Yindile Power Source Science and Technology Co., Ltd) 3.3 ml, intermittent 3 ml absolute ethyl alcohols and the 2ml distilled water of adding again, in agate mortar, manual mixing is ground 2.5h, is deployed into the slurry of certain viscosity.Deployed slurry is coated on the aluminium foil that 20 μ m are thick, makes the electrode slice that diameter is 1.2 cm with card punch.Under vacuum after 100 ℃ of oven dry, take Cellgard2400 as barrier film, LiPF
6solution is that electrolyte is assembled into 2032 button cells, charging/discharging voltage scope 3.3 ~ 5V, measures its specific discharge capacity at 0.2 C, 0.5 C, 1 C, 2 C, 6 C, 12C and 0.2C and is respectively 119.6 mAh/g, 120.5 mAh/g, 112.9 mAh/g, 104.8 mAh/g, 95.1 mAh/g, 75.5 mAh/g and 123 mAh/g; Then measure its charge and discharge cycles 200 times under 1 C, capability retention is 91.7%.Relatively show with the charging and discharging curve of comparative example 1 under 0.5 C, the charging voltage platform of embodiment 1 is low, and discharge voltage plateau is high, and efficiency for charge-discharge obviously improves; Show at the cyclic curve under different multiplying with comparative example 1, the high rate performance of embodiment 1 especially high rate capability obviously improves; 200 cyclic curves with comparative example 1 under 1 C relatively show, embodiment 1 has higher specific capacity, better capability retention.
According to the method described in embodiment 1, preparation PAALi.Take LiNi
0.5mn
1.5o
4finished product 4.8500 g, PAALi 0.150 g, in this mixture, PAALi mass fraction is 3 %.By the LiNi taking
0.5mn
1.5o
4, PAALi 0.150 g fully dissolves and is mixed in 5mL water, carries out tentatively moving to vacuum drying chamber in 100 ℃ of vacuumize 24h after stirring evaporation on electric jacket, obtains 5g LNM 3%PAALi powder sample.According to method preparation assembled battery described in embodiment 1, measure its specific discharge capacity at 0.2 C, 0.5 C, 1 C, 2 C, 6 C, 12C and 0.2C and be respectively 118.5 mAh/g, 116.7 mAh/g, 113.7 mAh/g, 110.6 mAh/g, 99.1 mAh/g, 84.6 mAh/g and 119.5 mAh/g; Then measure its charge and discharge cycles 200 times under 1 C, capability retention is 88.9%.
According to the method described in embodiment 1, preparation PAALi.Take LiNi
0.5mn
1.5o
4finished product 4.9500 g, PAALi 0.050 g, in this mixture, PAALi mass fraction is 1 %.By the LiNi taking
0.5mn
1.5o
4, PAALi 0.050 g fully dissolves and is mixed in 5mL water, carries out tentatively moving to vacuum drying chamber in 100 ℃ of vacuumize 24h after stirring evaporation on electric jacket, obtains 5g LNM 1%PAALi powder sample.According to method preparation assembled battery described in embodiment 1, measure its specific discharge capacity at 0.2 C, 0.5 C, 1 C, 2 C, 6 C, 12C and 0.2C and be respectively 125.5 mAh/g, 121.5 mAh/g, 117.3 mAh/g, 110.6 mAh/g, 96.3 mAh/g, 74.1 mAh/g and 122.7 mAh/g; Then measure its charge and discharge cycles 200 times under 1 C, capability retention is 84.3%.
Embodiment 4
According to the method described in embodiment 1, preparation PAALi.Take LiNi
0.5mn
1.5o
4finished product 4.9875 g, PAALi 0.0125 g, in this mixture, PAALi mass fraction is 0.25 %.By the LiNi taking
0.5mn
1.5o
4, PAALi 0.025g fully dissolves and is mixed in 5mL water, carries out tentatively moving to vacuum drying chamber in 100 ℃ of vacuumize 24h after stirring evaporation on electric jacket, obtains 5g LNM 0.25%PAALi powder sample.According to method preparation assembled battery described in embodiment 1, measure its specific discharge capacity at 0.2 C, 0.5 C, 1 C, 2 C, 6 C, 12C and 0.2C and be respectively 119.5 mAh/g, 118.6 mAh/g, 109.6 mAh/g, 104.1 mAh/g, 92 mAh/g, 78.4 mAh/g and 118.7 mAh/g; Then measure its charge and discharge cycles 200 times under 1 C, capability retention is 88.9%.
Comparison example 1
According to the method described in embodiment 1 only to LiNi
0.5mn
1.5o
4(without PAALi) is prepared and tests chemical property.Measure its specific discharge capacity at 0.2 C, 0.5 C, 1 C, 2 C, 6 C, 12 C and 02C and be respectively 122.1 mAh/g, 115.4 mAh/g, 110.4 mAh/g, 77.3 mAh/g, 49.6 mAh/g and 117.2 mAh/g; Then measure its charge and discharge cycles 200 times under 1 C, capability retention is 56.4 %.
Claims (8)
1. the coated LiNi of polyelectrolyte
0.5mn
1.5o
4the preparation method of positive electrode, is characterized in that, the coated LiNi of application polyelectrolyte solution
0.5mn
1.5o
4, the then dry coated LiNi of polyelectrolyte that obtains
0.5mn
1.5o
4, described polyelectrolyte is the mixture of a kind of or above several materials in Lithium polyacrylate, polymethylacrylic acid lithium, poly lithium, poly-(methyl vinyl ether copolymerization maleic acid) lithium or poly-fumaric acid lithium.
2. the coated LiNi of a kind of polyelectrolyte according to claim 1
0.5mn
1.5o
4the preparation method of positive electrode, is characterized in that, described polyelectrolyte solution is the polyelectrolyte aqueous solution or organic solution.
3. the coated LiNi of a kind of polyelectrolyte according to claim 2
0.5mn
1.5o
4the preparation method of positive electrode, is characterized in that: the aqueous solution that described polyelectrolyte solution is Lithium polyacrylate.
4. the coated LiNi of a kind of polyelectrolyte according to claim 3
0.5mn
1.5o
4the preparation method of positive electrode, is characterized in that: described Lithium polyacrylate is reacted and obtained or adopt Lithium acrylate polymerization to obtain by polymer chemistry.
5. the coated LiNi of a kind of polyelectrolyte according to claim 4
0.5mn
1.5o
4the preparation method of positive electrode, is characterized in that, specifically comprises the following steps:
(1) taking mean molecule quantity is 1000 ~ 4000000 polyacrylic acid, configuration LiOHH
2the O aqueous solution, dropwise joins LiOH solution in polyacrylic acid, until the pH value of solution is 8, above-mentioned gained solution is obtained to solid matter Lithium polyacrylate through pervaporation, after dry;
(2) take Lithium polyacrylate and LiNi
0.5mn
1.5o
4powder, the mixing that is dissolved in water, vacuumize, obtains the coated LiNi in Lithium polyacrylate surface
0.5mn
1.5o
4positive electrode.
6. the coated LiNi of a kind of polyelectrolyte according to claim 5
0.5mn
1.5o
4the preparation method of positive electrode, is characterized in that, specifically comprises the following steps:
(1) taking mean molecule quantity is that 3000 polyacrylic acid is in container, taking LiOHH2O is dissolved in distilled water and obtains LiOH solution, LiOH solution is dropwise joined in polyacrylic acid, until the pH value of solution is 8,80 ℃ of heating of gained solution are steamed to thick, then move to vacuum drying chamber in 100 ℃ of vacuumize 24 h, obtain white solid matter Lithium polyacrylate;
(2) take according to a certain percentage Lithium polyacrylate and the LiNi of certain mass
0.5mn
1.5o
4powder, adds distilled water to carry out fully dissolving and mixing, and moves to vacuumize vacuumize 24 h at 100 ℃ on electric jacket after tentatively evaporating, and obtains the coated LiNi in Lithium polyacrylate surface
0.5mn
1.5o
4positive electrode.
7. the coated LiNi of a kind of polyelectrolyte according to claim 4
0.5mn
1.5o
4the preparation method of positive electrode, is characterized in that, the coated part by weight of Lithium polyacrylate is 0.25～10%.
8. the coated LiNi of a kind of polyelectrolyte according to claim 7
0.5mn
1.5o
4the preparation method of positive electrode, is characterized in that, the coated part by weight of Lithium polyacrylate is 0.25～5%.
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| CN106981639A (en) * | 2017-05-11 | 2017-07-25 | 苏州大学 | A kind of preparation method of organic salt coated LiFePO 4 for lithium ion batteries positive electrode |
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| CN109273674A (en) * | 2018-07-31 | 2019-01-25 | 广东工业大学 | A kind of tertiary cathode material and its preparation method and application of Lithium polyacrylate cladding |
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