CN103872305B - The coated Li of polyelectrolyte 4ti 5o 12the preparation method of negative material - Google Patents

The coated Li of polyelectrolyte 4ti 5o 12the preparation method of negative material Download PDF

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CN103872305B
CN103872305B CN201410109282.9A CN201410109282A CN103872305B CN 103872305 B CN103872305 B CN 103872305B CN 201410109282 A CN201410109282 A CN 201410109282A CN 103872305 B CN103872305 B CN 103872305B
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polyelectrolyte
coated
lithium
negative material
preparation
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CN103872305A (en
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范未峰
王国冬
代洋杰
吴宗峻
黄新星
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Jiange County Ruixin Asset Management Co ltd
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SICHUAN XING NENG NEW MATERIALS Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • C01G23/003Titanates
    • C01G23/005Alkali titanates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses the coated Li of a kind of polyelectrolyte 4ti 5o 12?the preparation method of negative material, the coated Li of application polyelectrolyte solution 4ti 5o 12?, then drying obtains the coated Li of polyelectrolyte 4ti 5o 12?, described polyelectrolyte is the mixture of one or more several materials in Lithium polyacrylate, polymethylacrylic acid lithium, poly lithium, poly-(methyl vinyl ether copolymerization maleic acid) lithium or poly-fumaric acid lithium.This method for coating is at Li 4ti 5o 12?surface defines one deck polyelectrolyte film, enhances the compatibility with electrolyte, therefore has the feature of height ratio capacity, high magnification, long circulation life.

Description

The coated Li of polyelectrolyte 4ti 5o 12the preparation method of negative material
Technical field
The invention belongs to technical field of lithium ion battery negative, be specifically related to the coated Li of a kind of polyelectrolyte 4ti 5o 12the preparation method of negative material.
Background technology
Novel cathode material for lithium ion battery lithium titanate is " zero tension force " material, and battery life is extended greatly, and charge and discharge cycles can reach more than thousands of times.The lithium titanate anode material of new research and development and the novel battery group of manganate cathode material for lithium have been applied on the environment-friendly and green illuminator of wind light mutual complementing.The lithium battery that traditional solar street light is used for accumulate every two years will be changed once, and can reach 15 years useful life with the lithium battery that new material is made.Li 4ti 5o 12maximum feature is exactly its " zero strain ".
So-called " zero strain " refer to its crystal when embedding or deviate from lithium ion lattice constant and change in volume all very little, be less than 1%.In charge and discharge cycles, this " zero strain " can be avoided due to the flexible back and forth of electrode material and cause structural damage, thus improve cycle performance and the useful life of electrode, reduce the special capacity fade circulating and bring, there is extraordinary overcharging resisting, cross and put feature.
In addition because the catalytic action of Ti-O key in lithium titanate can aggravate the reaction of lithium titanate and electrolyte, cause the consumption of electrolyte, inside battery aerogenesis, cycle performance declines.
Summary of the invention
Deficiency for above-mentioned lithium titanate material of the present invention, proposes a kind of simple, quick polyelectrolyte Surface coating Li 4ti 5o 12the method of negative material, PAALi Surface coating Li prepared by the method 4ti 5o 12negative material has height ratio capacity, high magnification, long-life feature.
Technical scheme of the present invention: the coated Li of a kind of polyelectrolyte 4ti 5o 12the preparation method of negative material, the coated Li of application polyelectrolyte solution 4ti 5o 12, then drying obtains the coated Li of polyelectrolyte 4ti 5o 12, described polyelectrolyte is the mixture of one or more 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 aqueous solution or the organic solution of polyelectrolyte.
Further, described polyelectrolyte solution is the aqueous solution of Lithium polyacrylate.
Further, described Lithium polyacrylate is obtained by reacting by polymer chemistry or adopts Lithium acrylate polymerization to obtain.
Further, concrete preparation method is:
(1) take the polyacrylic acid that mean molecule quantity is 1000 ~ 4000000, add LiOHH 2the O aqueous solution, adjust ph is 8, and above-mentioned gained solution is obtained solid matter Lithium polyacrylate after pervaporation, drying;
(2) take the Lithium polyacrylate that step (1) obtains, be dissolved in the water, add Li 4ti 5o 12powder, vacuumize, obtains the coated Li of Lithium polyacrylate 4ti 5o 12negative material.
Further, concrete preparation method is:
(1) take mean molecule quantity be the polyacrylic acid of 3000 in container, take LiOHH 2o is dissolved in distilled water and obtains LiOH solution, LiOH dropwise is joined in polyacrylic acid, until the pH value of solution is 8, gained solution 80 DEG C heating is steamed to thick, then move to vacuum drying chamber in 100 DEG C of vacuumize 24h, obtain white solid matter Lithium polyacrylate;
(2) Lithium polyacrylate and the Li of certain mass is taken according to a certain percentage 4ti 5o 12powder, adds quantitative distilled water and fully dissolves mixing, moves to vacuumize vacuumize at 100 DEG C on electric jacket after tentatively evaporating, and obtains Lithium polyacrylate Surface coating Li 4ti 5o 12negative material.
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 ~ 10%.
The present invention compared with prior art has following technique effect:
1, the present invention by method for coating at Li 4ti 5o 12surface defines one deck polyelectrolyte film, enhances the compatibility with electrolyte, therefore has the feature of height ratio capacity, high magnification, long circulation life.
2, method of the present invention have simply, feature fast.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 and the charging and discharging curve of comparative example 1 under 0.5C compare;
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 1C multiplying power.
Embodiment
Embodiment 1
Taking mean molecule quantity is in polyacrylic acid 10.2g to the 200ml evaporating dish of 3000, takes LiOHH 2o2.32g, be dissolved in 36g distilled water and obtain LiOH solution, LiOH dropwise is joined in evaporating dish, until the pH value of solution is 8, above-mentioned gained solution is tentatively steamed to thick in electric jacket 80 DEG C, then mixture is moved to vacuum drying chamber in 100 DEG C of vacuumize 24h, obtain white solid matter PAALi.Take Li 4ti 5o 12finished product 4.975g, PAALi0.025g, in this mixture, PAALi mass fraction is 0.5%.By the Li taken 4ti 5o 12, PAALi0.025g fully dissolves and is mixed in 5mL water, electric jacket carries out preliminary stir evaporation after move to vacuum drying chamber in 100 DEG C of vacuumize 24h, obtain 5gLTO0.5%PAALi powder sample.
Take SuperP0.1g, LTO0.5%PAALi0.8g, solid content 3wt.% aqueous adhesive LA132(Chengdu Yindile Power Source Science and Technology Co., Ltd) 3.3ml, intermittently again add 3ml absolute ethyl alcohol and 2ml distilled water, in agate mortar, manual mixing grinding 2.5h, is deployed into the slurry of certain viscosity.Deployed slurry is coated on 20 μm of thick aluminium foils, makes with card punch the electrode slice that diameter is 1.2cm.Under vacuo after 100 DEG C of oven dry, take Cellgard2400 as barrier film, LiPF 6solution is that electrolyte is assembled into 2032 button cells, charging/discharging voltage scope 1 ~ 3V, measures it and is respectively 170mAh/g, 168mAh/g, 160mAh/g, 155mAh/g, 150mAh/g, 130mAh/g and 171mAh/g at the specific discharge capacity of 0.2C, 0.5C, 1C, 2C, 6C, 12C and 0.2C; Then measure its charge and discharge cycles 200 times under 1C, capability retention is 98%.Compare with the charging and discharging curve of comparative example 1 under 0.5C and show, the charging voltage platform of embodiment 1 is low, and discharge voltage plateau is high, and efficiency for charge-discharge significantly improves; Show with the cyclic curve of comparative example 1 under different multiplying, the high rate performance of embodiment 1 especially high rate capability significantly improves; Compare with 200 cyclic curves of comparative example 1 under 1C and show, embodiment 1 has higher specific capacity, better capability retention.
Embodiment 2
According to the method described in embodiment 1, preparation PAALi.Take Li 4ti 5o 12finished product 4.8500g, PAALi0.150g, in this mixture, PAALi mass fraction is 3%.By the Li taken 4ti 5o 12, PAALi0.150g fully dissolves and is mixed in 5mL water, electric jacket carries out preliminary stir evaporation after move to vacuum drying chamber in 100 DEG C of vacuumize 24h, obtain 5gLTO3%PAALi powder sample.According to the method preparation also assembled battery described in embodiment 1, measure it and be respectively 169mAh/g, 166mAh/g, 158mAh/g, 154mAh/g, 128mAh/g, 126mAh/g and 168mAh/g at the specific discharge capacity of 0.2C, 0.5C, 1C, 2C, 6C, 12C and 0.2C; Then measure its charge and discharge cycles 200 times under 1C, capability retention is 97,5%.
Embodiment 3
According to the method described in embodiment 1, preparation PAALi.Take Li 4ti 5o 12finished product 4.9500g, PAALi0.050g, in this mixture, PAALi mass fraction is 1%.By the Li taken 4ti 5o 12, PAALi0.050g fully dissolves and is mixed in 5mL water, electric jacket carries out preliminary stir evaporation after move to vacuum drying chamber in 100 DEG C of vacuumize 24h, obtain 5gLTO1%PAALi powder sample.According to the method preparation also assembled battery described in embodiment 1, measure it and be respectively 171mAh/g, 168mAh/g, 161mAh/g, 158mAh/g, 148mAh/g, 131mAh/g and 172mAh/g at the specific discharge capacity of 0.2C, 0.5C, 1C, 2C, 6C, 12C and 0.2C; Then measure its charge and discharge cycles 200 times under 1C, capability retention is 98%.
Embodiment 4
According to the method described in embodiment 1, preparation PAALi.Take Li 4ti 5o 12finished product 4.9875g, PAALi0.0125g, in this mixture, PAALi mass fraction is 0.25%.By the Li taken 4ti 5o 12, PAALi0.025g fully dissolves and is mixed in 5mL water, electric jacket carries out preliminary stir evaporation after move to vacuum drying chamber in 100 DEG C of vacuumize 24h, obtain 5gLTO0.25%PAALi powder sample.According to the method preparation also assembled battery described in embodiment 1, measure it and be respectively 168mAh/g, 165mAh/g, 156mAh/g, 152mAh/g, 145mAh/g, 128mAh/g and 168mAh/g at the specific discharge capacity of 0.2C, 0.5C, 1C, 2C, 6C, 12C and 0.2C; Then measure its charge and discharge cycles 200 times under 1C, capability retention is 97.2%.
Comparative example 1
According to the method described in embodiment 1 only to Li 4ti 5o 12(without PAALi) is prepared and tests chemical property.Measure it and be respectively 162mAh/g, 158mAh/g, 150mAh/g, 146mAh/g, 130mAh/g, 120mAh/g and 163mAh/g at the specific discharge capacity of 0.2C, 0.5C, 1C, 2C, 6C, 12C and 02C; Then measure its charge and discharge cycles 200 times under 1C, capability retention is 92.5%.

Claims (7)

1. the coated Li of polyelectrolyte 4ti 5o 12the preparation method of negative material, is characterized in that: the coated Li of application polyelectrolyte solution 4ti 5o 12, then drying obtains the coated Li of polyelectrolyte 4ti 5o 12, described polyelectrolyte is the mixture of one or more 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 Li of a kind of polyelectrolyte according to claim 1 4ti 5o 12the preparation method of negative material, is characterized in that: described polyelectrolyte solution is the aqueous solution or the organic solution of polyelectrolyte.
3. the coated Li of a kind of polyelectrolyte according to claim 2 4ti 5o 12the preparation method of negative material, is characterized in that: described polyelectrolyte solution is the aqueous solution of Lithium polyacrylate.
4. the coated Li of a kind of polyelectrolyte according to claim 3 4ti 5o 12the preparation method of negative material, is characterized in that: described Lithium polyacrylate is obtained by reacting by polymer chemistry or adopts Lithium acrylate to be polymerized and obtains.
5. the coated Li of a kind of polyelectrolyte according to claim 4 4ti 5o 12the preparation method of negative material, is characterized in that:
(1) take the polyacrylic acid that mean molecule quantity is 1000 ~ 4000000, add LiOHH 2the O aqueous solution, adjust ph is 8, and above-mentioned gained solution is obtained solid matter Lithium polyacrylate after pervaporation, drying;
(2) take the Lithium polyacrylate that step (1) obtains, be dissolved in the water, add Li 4ti 5o 12powder, vacuumize, obtains the coated Li of Lithium polyacrylate 4ti 5o 12negative material.
6. the coated Li of a kind of polyelectrolyte according to claim 5 4ti 5o 12the preparation method of negative material, is characterized in that: specifically comprise the following steps:
(1) take mean molecule quantity be the polyacrylic acid of 3000 in container, take LiOHH 2o is dissolved in distilled water and obtains LiOH solution, LiOH dropwise is joined in polyacrylic acid, until the pH value of solution is 8, gained solution 80 DEG C heating is steamed to thick, then move to vacuum drying chamber in 100 DEG C of vacuumize 24h, obtain white solid matter Lithium polyacrylate;
(2) Lithium polyacrylate and the Li of certain mass is taken according to a certain percentage 4ti 5o 12powder, adds quantitative distilled water and fully dissolves mixing, moves to vacuumize vacuumize at 100 DEG C on electric jacket after tentatively evaporating, and obtains Lithium polyacrylate Surface coating Li 4ti 5o 12negative material.
7. the coated Li of a kind of polyelectrolyte according to claim 5 or 6 4ti 5o 12the preparation method of negative material, is characterized in that: the coated part by weight of Lithium polyacrylate is 0.25 ~ 10%.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN101373829A (en) * 2008-10-07 2009-02-25 深圳市贝特瑞新能源材料股份有限公司 Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery
CN101431154A (en) * 2008-12-25 2009-05-13 成都中科来方能源科技有限公司 Lithium titanate/C composite electrode material and method for producing the same
CN102522563A (en) * 2011-12-30 2012-06-27 中国科学院广州能源研究所 Conducting-polymer dipped and coated lithium-ion battery composite-electrode material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US7875388B2 (en) * 2007-02-06 2011-01-25 3M Innovative Properties Company Electrodes including polyacrylate binders and methods of making and using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101373829A (en) * 2008-10-07 2009-02-25 深圳市贝特瑞新能源材料股份有限公司 Titanium-series cathode active material and preparation method thereof, titanium-series lithium ion power battery
CN101431154A (en) * 2008-12-25 2009-05-13 成都中科来方能源科技有限公司 Lithium titanate/C composite electrode material and method for producing the same
CN102522563A (en) * 2011-12-30 2012-06-27 中国科学院广州能源研究所 Conducting-polymer dipped and coated lithium-ion battery composite-electrode material and preparation method thereof

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