CN110061212A - The modified nickelic layered cathode material of garnet-type solid electrolyte and preparation method - Google Patents

The modified nickelic layered cathode material of garnet-type solid electrolyte and preparation method Download PDF

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Publication number
CN110061212A
CN110061212A CN201910306941.0A CN201910306941A CN110061212A CN 110061212 A CN110061212 A CN 110061212A CN 201910306941 A CN201910306941 A CN 201910306941A CN 110061212 A CN110061212 A CN 110061212A
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China
Prior art keywords
cathode material
solid electrolyte
layered cathode
garnet
type solid
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CN201910306941.0A
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Inventor
李栋
雷超
皮琳
安钰叶
赖华
林占康
钟盛文
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Jiangxi University of Science and Technology
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Jiangxi University of Science and Technology
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Priority to CN201910306941.0A priority Critical patent/CN110061212A/en
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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
    • 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
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/36—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
    • H01M4/624—Electric conductive 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)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention provides a kind of modified nickelic layered cathode material of garnet-type solid electrolyte and preparation methods, the following steps are included: the garnet-type solid electrolyte powder prepared using solid phase method is added in ball grinder, add appropriate grinding aid, garnet-type solid electrolyte powder is mixed with the abundant ball milling of nickelic layered cathode material, obtains the modified nickelic layered cathode material of garnet-type solid electrolyte after dry.The introducing that the present invention passes through garnet-type solid electrolyte, good conductive network is formd in the inside of high-nickel material, while reducing the internal resistance of cell, promoting the super large rate charge-discharge performance and cycle performance of material, the high capacity characteristics for having given full play of nickelic layered cathode material improve the comprehensive electrochemical of battery.

Description

The modified nickelic layered cathode material of garnet-type solid electrolyte and preparation method
Technical field
The invention belongs to field of batteries, and in particular to one kind have high conductance, low internal resistance, high magnification, macrocyclic lithium from Sub- cell positive material and preparation method thereof.
Background technique
There are Ni for nickel element2+-Ni3+-Ni4+Multivalent state variation, thus in nickelic layered cathode material in charge and discharge process Show high charging and discharging capacity and specific energy, and stratiform cell positive material can be provided for the deintercalation of lithium ion it is good Diffusion admittance has big lithium ion diffusion coefficient, the high rate performance having had.However the introducing of nickel element is promoting material ratio While capacity, so that material produces defect to a certain extent: electrolyte is easily by the oxidation of high price nickel, nickel multivalent state bring Material structure phase transformation, material surface easily form high impedance phase Li2CO3, lead to the cyclical stability of battery difference, thermal stability and again Rate performance.
Surface modification adheres to layer of substance on positive electrode surface, such as: conductive carbon, carbon nanocoils, class graphene carbon, MgO、Al2O3、ZrO2、Cr2O3、Li2TiO3、LiAlO2Deng being effectively prevented from directly contacting for material and electrolyte, mitigate electrolysis Oxidation of the liquid to the corrosion and high price nickel of positive electrode to electrolyte, keep material and electrolyte in cyclic process structure it is complete It is whole and stable, improve the service life of battery, and the electric conductivity of positive electrode can be improved to a certain extent.But it was modified Generally existing modified technique is complicated in journey, modified material is difficult to disperse, conductivity promotes the series of problems such as limited, needs further Optimization.
Summary of the invention
For the above problem existing for nickeliferous layered cathode material, the present invention provides a kind of garnet-type solid electrolytes Modified nickelic layered cathode material and preparation method thereof, by the introducing of garnet-type solid electrolyte, in high-nickel material Inside forms good conductive network, in the super large rate charge-discharge performance and cyclicity for reducing the internal resistance of cell, promoting material While energy, the high capacity characteristics of nickelic layered cathode material are given full play of, the comprehensive electrochemical of battery is improved.
The modified nickelic layered cathode material and preparation method thereof of garnet-type solid electrolyte, it is characterised in that including with Lower step:
(1) the solid electrolyte powder that solid phase method is prepared is added in ball grinder, and grinding aid is added, ball milling 2-6h；
(2) increase nickel layered cathode material into ball grinder, ball milling 5-12h, abundant ball milling mixing is uniform；
(3) after uniformly mixed slurry is dry at 60-100 DEG C, the nickelic layered cathode material of modification after being dried.
2, it is required according to power 1, the solid electrolyte powder in step 1 are as follows: Li6+xLa5-y-z-zZryTazMzO12, 0 < x≤1,0 < y+z+z '≤4.5, wherein M can be independently selected from Nb, W, Ti, Hf, Ru, Mo, Nd, Ba, Ga, In, Ge, Sn, Sb, Se one kind or It is several.
3, required according to power 1, the grinding aid in step 1 are as follows: neopelex, sodium citrate, triethanolamine, Primary amine, methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, N-Methyl pyrrolidone.
4, it is required according to power 1, the nickelic layered cathode material in step 2 are as follows: LiNi0.55+xCoyM0.45-x-yO2, 0≤x < 0.45,0≤y≤0.45, wherein M can be independently selected from the one or more of Mn, Al, Fe, Zn, Zr, Cr, Mo, Y, Nd, Ga, Ge.
Advantages of the present invention: (1) it by the introducing of garnet-type solid electrolyte, is formd in the inside of high-nickel material good Good conductive network, reduces the internal resistance of battery, improves the high rate performance and cycle performance of material.(2) electrolyte is modified Nickelic layered cathode material in the charge and discharge process of 20C multiplying power, maintain good structural stability, give full play of The high capacity characteristics of nickelic layered cathode material improve the comprehensive electrochemical of battery.(3) modified technique is simple, convenient for big Large-scale production application.
Detailed description of the invention
The Li synthesized in Fig. 1 embodiment 16.4La3Zr1.4Ta0.6O12、LiNi0.8Mn0.1Co0.1O2And the object of modified material Phasor
The modified LiNi of the 5wt.%LLZTO that Fig. 2 embodiment 1 is prepared0.8Mn0.1Co0.1O2Shape appearance figure
The modified LiNi of the 1wt.%LLZTO that Fig. 3 embodiment 1 is prepared0.8Mn0.1Co0.1O2Cyclic voltammetry curve figure
The modified LiNi of the 1wt.%LLZTO that Fig. 4 embodiment 1 is prepared0.8Mn0.1Co0.1O2High rate performance
The modified LiNi of the 3wt.%LLZTGNO that Fig. 5 embodiment 2 is prepared0.8Co0.1Al0.1O2Ultra-high magnifications cycle performance.
Specific embodiment
The technical solution in embodiment of the present invention will be clearly and completely described, but is not limited to following below Embodiment.Based on the embodiment in the present invention, those skilled in the art are obtained without creative efforts Every other embodiment, shall fall within the protection scope of the present invention.
Embodiment 1
(1) the solid electrolyte powder Li for preparing solid phase method6.4La3Zr1.4Ta0.6O12It is added in ball grinder, and poly- first is added Base pyrrolidones, ball milling 2h；
(2) increase nickel layered cathode material LiNi0.8Mn0.1Co0.1O2Into ball grinder, ball milling 6h, abundant ball milling mixing is uniform；
(3) after uniformly mixed slurry is dry at 80 DEG C, the nickelic layered cathode material of modification after being dried.
Embodiment 2
(1) the solid electrolyte powder Li for preparing solid phase method6.4La3Zr1.4Ta0.2Ge0.1Nb0.3O12It is added in ball grinder, and Isopropanol, ball milling 5h is added；
(2) increase nickel layered cathode material LiNi0.8Co0.1Al0.1O2Into ball grinder, ball milling 8h, abundant ball milling mixing is uniform；
(3) after uniformly mixed slurry is dry at 70 DEG C, the nickelic layered cathode material of modification after being dried.
Embodiment 3
(1) the solid electrolyte powder Li for preparing solid phase method6La3Zr1.4Ta0.2W0.4O12It is added in ball grinder, and is added three Ethanol amine, ball milling 6h；
(2) increase nickel layered cathode material LiNi0.6Mn0.2Co0.2O2Into ball grinder, ball milling 10h, abundant ball milling mixing is uniform；
(3) after uniformly mixed slurry is dry at 85 DEG C, the nickelic layered cathode material of modification after being dried.
Embodiment 4
(1) the solid electrolyte powder Li for preparing solid phase method6.5La3Zr1.4Ta0.4Ga0.1W0.1O12It is added in ball grinder, and N-butanol, ball milling 4.5h is added；
(2) increase nickel layered cathode material LiNi0.8Co0.05Fe0.05Al0.1O2Into ball grinder, ball milling 11h, abundant ball milling mixing Uniformly；
(3) after uniformly mixed slurry is dry at 75 DEG C, the nickelic layered cathode material of modification after being dried.
The preparation of battery positive pole piece: by the black and poly- inclined tetrafluoro second of the positive electrode, the conductive acetylene that are synthesized in embodiment 1-4 Alkene (PVDF) is mixed by mass fraction ratio 85:10:5, and ball milling is coated on aluminium foil after appropriate pyrrolidones is added, and 120 DEG C The positive plate that diameter is 12mm is made to roller backlash in lower drying.
Battery assembly and test: cathode, 1M LiPF are made using metal Li piece6/ ethylene carbonate (EC)+dimethyl carbonic acid Ester (DMC)+diethyl carbonate (DEC) (volume ratio=1:1:1) is used as electrolyte, and diaphragm is microporous polypropylene membrane Celgard2300 is assembled into CR2032 type button cell in the glove box of argon atmosphere.

Claims (4)

1. the modified nickelic layered cathode material and preparation method thereof of garnet-type solid electrolyte, it is characterised in that including following Step:
(1) the solid electrolyte powder that solid phase method is prepared is added in ball grinder, and grinding aid is added, ball milling 2-6h；
(2) increase nickel layered cathode material into ball grinder, ball milling 5-12h, abundant ball milling mixing is uniform；
(3) after uniformly mixed slurry is dry at 60-100 DEG C, the nickelic layered cathode material of modification after being dried.
2. being required according to right 1, the solid electrolyte powder in step 1 are as follows: Li6+xLa5-y-z-z′ZryTazMz′O12, 0 < x≤1,0 < y+ Z+z '≤4.5, wherein M can be independently selected from one kind or several of Nb, W, Ti, Hf, Ru, Mo, Nd, Ba, Ga, In, Ge, Sn, Sb, Se Kind.
3. being required according to right 1, the grinding aid in step 1 are as follows: neopelex, sodium citrate, triethanolamine, primary Amine, methanol, ethyl alcohol, propyl alcohol, isopropanol, n-butanol, isobutanol, N-Methyl pyrrolidone.
4. being required according to right 1, the nickelic layered cathode material in step 2 are as follows: LiNi0.55+xCoyM0.45-x-yO2, 0≤x < 0.45, 0≤y≤0.45, wherein M can be independently selected from the one or more of Mn, Al, Fe, Zn, Zr, Cr, Mo, Y, Nd, Ga, Ge.
CN201910306941.0A 2019-04-17 2019-04-17 The modified nickelic layered cathode material of garnet-type solid electrolyte and preparation method Pending CN110061212A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113745457A (en) * 2020-05-27 2021-12-03 北京卫蓝新能源科技有限公司 High-safety and high-capacity positive pole piece for lithium battery and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108206277A (en) * 2016-12-20 2018-06-26 宁德时代新能源科技股份有限公司 Modified high-nickel ternary cathode material, preparation method thereof and lithium ion battery
CN108963202A (en) * 2018-05-28 2018-12-07 天津国安盟固利新材料科技股份有限公司 A kind of ternary layered positive electrode of high temperature modification and its preparation and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108206277A (en) * 2016-12-20 2018-06-26 宁德时代新能源科技股份有限公司 Modified high-nickel ternary cathode material, preparation method thereof and lithium ion battery
CN108963202A (en) * 2018-05-28 2018-12-07 天津国安盟固利新材料科技股份有限公司 A kind of ternary layered positive electrode of high temperature modification and its preparation and application

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李帅鹏等: "正极材料包覆改性对NCM523 /PEO/金属锂固态电池的性能优化", 《电子元件与材料》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113745457A (en) * 2020-05-27 2021-12-03 北京卫蓝新能源科技有限公司 High-safety and high-capacity positive pole piece for lithium battery and preparation method and application thereof
CN113745457B (en) * 2020-05-27 2023-07-28 北京卫蓝新能源科技有限公司 High-safety high-capacity positive electrode plate for lithium battery and preparation method and application thereof

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