CN108288694A - A kind of Mg2+Adulterate AlF3Coat the preparation method of tertiary cathode material - Google Patents

A kind of Mg2+Adulterate AlF3Coat the preparation method of tertiary cathode material Download PDF

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Publication number
CN108288694A
CN108288694A CN201711489354.7A CN201711489354A CN108288694A CN 108288694 A CN108288694 A CN 108288694A CN 201711489354 A CN201711489354 A CN 201711489354A CN 108288694 A CN108288694 A CN 108288694A
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cathode material
tertiary cathode
alf
adulterate
preparation
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孙旭
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JIANGSU KING LITHIUM CELL CO Ltd
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JIANGSU KING LITHIUM CELL CO Ltd
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/48—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • 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)
  • Inorganic Chemistry (AREA)
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  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of Mg2+Adulterate AlF3Coat the preparation method of tertiary cathode material.This approach includes the following steps：1）By Ni0.5Co0.2Mn0.3（OH）2、Li2CO3Mixing；2）By step 1）In mixture sintering after obtain tertiary cathode material LiNi0.5Co0.2Mn0.3O2；3）By step 2）In obtained tertiary cathode material and basic magnesium carbonate mixing, sintering obtain mixing the tertiary cathode material of Mg2+；4）Again by step 3）In mix Mg2+Tertiary cathode material be added Al (NO3) 3 solution in disperseed, NH is slowly added dropwise inwards4F solution, the solution persistently stir 2h in 80 DEG C of water-baths, then filter, dry；5）By step 4）Material after middle drying is sintered to obtain Mg2+Adulterate AlF3The tertiary cathode material of cladding.The present invention is modified tertiary cathode material by adulterating and coating, and the high rate performance of material and cycle performance is made to significantly improve, and low cost and high performance anode material for lithium-ion batteries can be obtained.

Description

A kind of Mg2+Adulterate AlF3Coat the preparation method of tertiary cathode material
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, specifically a kind of Mg2+Adulterate AlF3Cladding The preparation method of tertiary cathode material.
Background technology
Tertiary cathode material Li（Ni0.5Co0.2Mn0.3）O2As anode material for lithium-ion batteries, electric discharge low with price The features such as specific capacity height, stable circulation.However the limitation of existing anode material for lithium-ion batteries one side material itself makes Performance has been difficult to be improved again, still further aspect, and there is also certain defects by preparation process.So that existing ternary is just There is high rate performance, high-temperature storage performance and the bad defects of cycle performance for pole material.
Invention content
Technical problem to be solved by the invention is to provide a kind of high rate performance that can improve tertiary cathode material, high temperature The Mg of storge quality and cycle performance2+Adulterate AlF3Coat the preparation method of tertiary cathode material.
In order to solve the above-mentioned technical problem, Mg of the invention2+Adulterate AlF3Coat the preparation method of tertiary cathode material, packet Include following steps：
（1）By Ni0.5Co0.2Mn0.3（OH）2、Li2CO3The molar ratio of mixing, lithium carbonate and ternary precursor is 1.03-1.06；
（2）By step（1）In mixture after mixing, be sintered 9- at a temperature of 850-950 DEG C in air Muffle furnace 12h is crushed sieving after cooling and obtains tertiary cathode material LiNi0.5Co0.2Mn0.3O2；
（3）By step（2）In obtained tertiary cathode material and basic magnesium carbonate according to stoichiometric ratio Mg2+/M=0.003- 0.005 uniformly mixing, wherein M is Ni, Co, Mn total content；
（4）The material mixed is subjected to double sintering in air Muffle furnace, then with furnace temperature natural cooling, is crushed, sieving obtains To mixing Mg2+Tertiary cathode material；
（5）Again by step（4）In mix Mg2+Tertiary cathode material Al (NO are added3)3Disperseed in solution, and is slowly dripped Add NH4F solution, AlF in solution3Amount be tertiary cathode material 0.5-1%, which persistently stirs in 70-80 DEG C of water-bath 2-3h is mixed, is then filtered, it is dry；
（6）By step（5）Material after middle drying roasts furnace cooling after 4-6h at 430-470 DEG C, is crushed after taking-up, mistake Sieve, obtains AlF3Cladding mixes Mg2+Tertiary cathode material.
The step（1）The molar ratio of middle lithium carbonate and ternary precursor is 1.04.
The step（2）Middle sintering temperature is 940 DEG C, soaking time 10h.
The step（3）Middle Mg2+/M=0.004。
The step（4）AlF in middle solution3Amount be tertiary cathode material 0.8%.
After adopting with the aforedescribed process, dexterously Mg2+Doping and AlF3Cladding, on this basis, will obtain in preparation process Tertiary cathode material and basic magnesium carbonate mixing after carry out double sintering and reasonably control the condition of sintering obtaining mixing Mg2+ Tertiary cathode material, in addition will mix Mg2+Tertiary cathode material Al (NO are added3)3Dispersion is carried out in solution by special Technique obtains AlF3Cladding mixes Mg2+Tertiary cathode material so that high rate performance and cycle performance significantly improves and it Rational process so that manufacturing cost is very low.
Specific implementation mode
With reference to embodiment, to the Mg of the present invention2+Adulterate AlF3Coat the preparation side of 523 tertiary cathode materials Method is described in further detail.
Embodiment one：
The Mg of the present invention2+Adulterate AlF3The preparation method for coating tertiary cathode material, includes the following steps：
（1）By Ni0.5Co0.2Mn0.3（OH）2、Li2CO3The molar ratio of mixing, lithium carbonate and ternary precursor is 1.03；
（2）By step（1）In mixture after mixing, 9h is sintered at 850 DEG C in air Muffle furnace, was crushed after cooling Sieve obtains tertiary cathode material LiNi0.5Co0.2Mn0.3O2；
（3）By step（2）In obtained tertiary cathode material and basic magnesium carbonate in three-dimensional material mixer according to stoichiometric ratio Mg2+/M=0.003（Wherein, M is Ni, Co, Mn total content）Uniformly mixing,
（4）The material mixed is subjected to double sintering in air Muffle furnace, sintering process is the heating from room temperature to 600 DEG C 3 DEG C/min of rate, from 600 DEG C to 800 DEG C, 1 DEG C/min of heating rate keeps the temperature 9 h, then with stove under 800 DEG C of temperature environments Warm natural cooling is crushed, and sieving obtains mixing Mg2+Tertiary cathode material；
（5）Again by step（4）In mix Mg2+Tertiary cathode material Al (NO are added3)3Disperseed in solution, inwards slowly NH is added dropwise4The molar ratio of F solution, control Al and F is 1:3, AlF in solution3Amount be tertiary cathode material 0.5% (mole point Number）, which persistently stirs 2h in 70 DEG C of water-baths, then filters, dry；
（6）By step（5）Material after middle drying roasts furnace cooling after 4h at 430 DEG C, is crushed after taking-up, and sieving obtains AlF3Cladding mixes Mg2+Tertiary cathode material.
Embodiment two：
The Mg of the present invention2+Adulterate AlF3The preparation method for coating tertiary cathode material, includes the following steps：
（1）By Ni0.5Co0.2Mn0.3（OH）2、Li2CO3The molar ratio of mixing, lithium carbonate and ternary precursor is 1.04；
（2）By step（1）In mixture after mixing, 10h is sintered at 940 DEG C in air Muffle furnace, is crushed after cooling Sieving obtains tertiary cathode material LiNi0.5Co0.2Mn0.3O2；
（3）By step（2）In obtained tertiary cathode material and basic magnesium carbonate in three-dimensional material mixer according to stoichiometric ratio Mg2+/M=0.004（Wherein, M is Ni, Co, Mn total content）Uniformly mixing,
（4）The material mixed is subjected to double sintering in air Muffle furnace, sintering process is the heating from room temperature to 600 DEG C 4 DEG C/min of rate, from 600 DEG C to 800 DEG C, 1.2 DEG C/min of heating rate keeps the temperature 10h under 850 DEG C of temperature environments, then with Furnace temperature natural cooling is crushed, and sieving obtains mixing Mg2+Tertiary cathode material；
（5）Again by step（4）In mix Mg2+Tertiary cathode material Al (NO are added3)3Disperseed in solution, inwards slowly NH is added dropwise4The molar ratio of F solution, control Al and F is 1:3, AlF in solution3Amount be tertiary cathode material 0.8% (mole point Number）, which persistently stirs 2.5h in 70-80 DEG C of water-bath, then filters, dry；
（6）By step（5）Material after middle drying roasts furnace cooling after 5h at 450 DEG C, is crushed after taking-up, and sieving obtains AlF3Cladding mixes Mg2+Tertiary cathode material.
Embodiment three：
The Mg of the present invention2+Adulterate AlF3The preparation method for coating tertiary cathode material, includes the following steps：
（1）By Ni0.5Co0.2Mn0.3（OH）2、Li2CO3The molar ratio of mixing, lithium carbonate and ternary precursor is 1.06；
（2）By step（1）In mixture after mixing, 12h is sintered at 950 DEG C in air Muffle furnace, is crushed after cooling Sieving obtains tertiary cathode material LiNi0.5Co0.2Mn0.3O2；
（3）By step（2）In obtained tertiary cathode material and basic magnesium carbonate in three-dimensional material mixer according to stoichiometric ratio Mg2+/M=0.005（Wherein, M is Ni, Co, Mn total content）Uniformly mixing,
（4）The material mixed is subjected to double sintering in air Muffle furnace, sintering process is the heating from room temperature to 600 DEG C 5 DEG C/min of rate, from 600 DEG C to 800 DEG C, 1.5 DEG C/min of heating rate keeps the temperature 11 h under 900 DEG C of temperature environments, then with Furnace temperature natural cooling is crushed, and sieving obtains mixing Mg2+Tertiary cathode material；
（5）Again by step（4）In mix Mg2+Tertiary cathode material Al (NO are added3)3Disperseed in solution, inwards slowly NH is added dropwise4The molar ratio of F solution, control Al and F is 1:3, AlF in solution3Amount be tertiary cathode material 1% (mole point Number）, which persistently stirs 3h in 70-80 DEG C of water-bath, then filters, dry；
（6）By step（5）Material after middle drying roasts furnace cooling after 6h at 470 DEG C, is crushed after taking-up, and sieving obtains AlF3Cladding mixes Mg2+Tertiary cathode material.

Claims (6)

1. a kind of Mg2+Adulterate AlF3The preparation method for coating tertiary cathode material, includes the following steps：
（1）By Ni0.5Co0.2Mn0.3（OH）2、Li2CO3The molar ratio of mixing, lithium carbonate and ternary precursor is 1.03-1.06；
（2）By step（1）In mixture after mixing, be sintered 9- at a temperature of 850-950 DEG C in air Muffle furnace 12h is crushed sieving after cooling and obtains tertiary cathode material LiNi0.5Co0.2Mn0.3O2；
（3）By step（2）In obtained tertiary cathode material and basic magnesium carbonate according to stoichiometric ratio Mg2+/M=0.003- 0.005 uniformly mixing, wherein M is Ni, Co, Mn total content；
（4）The material mixed is subjected to double sintering in air Muffle furnace, then with furnace temperature natural cooling, is crushed, sieving obtains To mixing Mg2+Tertiary cathode material；
（5）Again by step（4）In mix Mg2+Tertiary cathode material Al (NO are added3)3Disperseed in solution, and is slowly added dropwise NH4F solution, AlF in solution3Amount be tertiary cathode material 0.5-1%, which persistently stirs in 70-80 DEG C of water-bath Then 2-3h is filtered, dry；
（6）By step（5）Material after middle drying roasts furnace cooling after 4-6h at 430-470 DEG C, is crushed after taking-up, mistake Sieve, obtains AlF3Cladding mixes Mg2+Tertiary cathode material.
2. Mg according to claim 12+Adulterate AlF3The preparation method of tertiary cathode material is coated, it is characterized in that：It is described Step（4）Middle double sintering process is 3-5 DEG C of the heating rate/min from room temperature to 600 DEG C, from 600 DEG C to 800 DEG C, is risen 1-1.5 DEG C of warm rate/min keeps the temperature 9-11 h under 800-900 DEG C of temperature environment, then with furnace temperature natural cooling, is crushed, sieving, It obtains mixing Mg2+Tertiary cathode material.
3. Mg according to claim 1 or 22+Adulterate AlF3The preparation method of tertiary cathode material is coated, it is characterized in that：Institute State step（1）The molar ratio of middle lithium carbonate and ternary precursor is 1.04.
4. Mg according to claim 32+Adulterate AlF3The preparation method of tertiary cathode material is coated, it is characterized in that：It is described Step（2）Middle sintering temperature is 940 DEG C, soaking time 10h.
5. Mg according to claim 42+Adulterate AlF3The preparation method of tertiary cathode material is coated, it is characterized in that：It is described Step（3）Middle Mg2+/M=0.004。
6. Mg according to claim 52+Adulterate AlF3The preparation method of tertiary cathode material is coated, it is characterized in that：It is described Step（4）AlF in middle solution3Amount be tertiary cathode material 0.8%.
CN201711489354.7A 2017-12-30 2017-12-30 A kind of Mg2+Adulterate AlF3Coat the preparation method of tertiary cathode material Pending CN108288694A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101154727A (en) * 2007-09-14 2008-04-02 中南大学 Coating method of porous clad material for effectively improving rate performance of lithium nickel cobalt manganese oxygen
CN103500827A (en) * 2013-10-11 2014-01-08 宁德新能源科技有限公司 Lithium ion battery and multi-element positive material thereof as well as preparation method of multi-element positive material
CN105958017A (en) * 2016-05-10 2016-09-21 山东玉皇新能源科技有限公司 Preparation method for aluminum-fluoride-coated lithium nickel cobalt manganate positive electrode material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101154727A (en) * 2007-09-14 2008-04-02 中南大学 Coating method of porous clad material for effectively improving rate performance of lithium nickel cobalt manganese oxygen
CN103500827A (en) * 2013-10-11 2014-01-08 宁德新能源科技有限公司 Lithium ion battery and multi-element positive material thereof as well as preparation method of multi-element positive material
CN105958017A (en) * 2016-05-10 2016-09-21 山东玉皇新能源科技有限公司 Preparation method for aluminum-fluoride-coated lithium nickel cobalt manganate positive electrode material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KAI YANG等: ""Significant improvement of electrochemical properties of AlF3-coated LiNi0.5Co0.2Mn0.3O2 cathode materials"", 《ELECTROCHIMICA ACTA》 *

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Application publication date: 20180717