CN104835956A - Method of preparing lithium ion battery anode material from two or more metal salts/solutions of nickel, cobalt, manganese, aluminum and the like - Google Patents

Method of preparing lithium ion battery anode material from two or more metal salts/solutions of nickel, cobalt, manganese, aluminum and the like Download PDF

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Publication number
CN104835956A
CN104835956A CN201510021393.9A CN201510021393A CN104835956A CN 104835956 A CN104835956 A CN 104835956A CN 201510021393 A CN201510021393 A CN 201510021393A CN 104835956 A CN104835956 A CN 104835956A
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China
Prior art keywords
manganese
cobalt
nickel
slaine
lithium
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CN201510021393.9A
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肖丹
郭勇
林朝红
张永志
陈立
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Sichuan University
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Sichuan University
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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
    • 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
    • H01M4/52—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
    • 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

To a lithium ion battery, LiNi<x>Co<y>Mn<z>M<1-x-y-z>O<2> is a potential anode material. The invention discloses a method of preparing the LiNi<x>Co<y>Mn<z>M<1-x-y-z>O<2>. In the method, a mixed solution of a precipitation agent and hydrogen peroxide are reacted with two or more metal salts/solutions of nickel, cobalt, manganese, aluminum and the like to obtain a precursor, Ni<x>Co<y>Mn<z>M<1-x-y-z>(OH)<2>, of the LiNi<x>Co<y>Mn<z>M<1-x-y-z>O<2>. In the synthetic process of the precursor, the hydrogen peroxide is employed as an oxidant for oxidizing metal ions so that the stability of the material is improved and the specific capacity of the material is increased. Meanwhile, oxygen generated through decomposition is employed as a dispersing agent for reducing agglomeration of the material. In addition, during a thermal treatment process, ozone atmosphere is employed for the thermal treatment of the material, thereby further oxidizing the metal ions in the material and improving the performance of the material. According to the invention, by means of the reaction between the two or more metal salts/solutions of nickel, cobalt, manganese, aluminum and the like and the precipitation agent with addition of the hydrogen peroxide to the precipitation agent and with the ozone added to the thermal treatment process, the LiNi<x>Co<y>Mn<z>M<1-x-y-z>O<2> is increased in the specific capacity and is enhanced in circulating stability when being used as the lithium ion battery anode material.

Description

A kind of by nickel, cobalt, manganese, aluminium etc. wherein two or more slaine/solution prepare the method for anode material for lithium-ion batteries
Technical field
The present invention relates to anode material for lithium-ion batteries, particularly utilize in precipitation reagent and add H 2o 2as additive metal ion in material be oxidized and material is disperseed, also relating to simultaneously and adopt O in heat treatment process 3material is further oxidized.
Background technology
Lithium ion battery is application and the best a kind of power supply of DEVELOPMENT PROSPECT, and its advantageous is high in operating voltage, and energy density is high, and the aspect such as have extended cycle life.The key improving performance of lithium ion battery is the performance improving anode material for lithium-ion batteries.In recent years, both at home and abroad for by nickel, cobalt, manganese, aluminium wherein two or more slaine/solution prepare anode material for lithium-ion batteries and give increasing concern, wish can by nickel, cobalt, manganese, aluminium etc. wherein two or more slaine/solution prepare have that specific capacity is high, the anode material for lithium-ion batteries of good cycle, the advantage such as to be easy to get with low cost.Therefore, study that wherein two or more slaines prepare anode material for lithium-ion batteries is an important job by various metals salt/solution such as nickel, cobalt, manganese, aluminium.
Existing multiple method for the synthesis of (0<x+y+z≤1; M:Al, Fe, Zn ...), as solid phase method, coprecipitation, hydrothermal synthesis method, sol-gel process and microemulsion method etc.Meanwhile, many Surface coating, the method for doping vario-property is used to improve the specific capacity of material, high rate performance and stability etc.But these improvement too increase more process, and employ more adding material.Because coprecipitation is easy to operate and be easy to suitability for industrialized production, therefore it is that to obtain chemical property good one of the most frequently used method.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of by nickel, cobalt, manganese, aluminium etc. wherein two or more slaine/solution prepare the method for anode material for lithium-ion batteries, the method can improve specific capacity and the cyclical stability of anode material for lithium-ion batteries effectively.The process employs the cheap and easy to get and H of environmental protection 2o 2as additive, and utilize O in heat treatment process 3carry out further oxidizing metal ions, thus it is good to obtain chemical property positive electrode.
The technical solution adopted for the present invention to solve the technical problems is: by nickel, cobalt, manganese, aluminium etc. wherein two or more slaine/solution prepare anode material for lithium-ion batteries, it is characterized in that: by the same nickel of mixed solution, cobalt, manganese, aluminium etc. of precipitation reagent and hydrogen peroxide wherein two or more slaine/solution react, obtain Ni xco ymn zm 1-x-y-z(OH) 2presoma; At Ni xco ymn zm 1-x-y-z(OH) 2in the process of heat-treating, be in O 3in environment.
As a kind of scheme of the present invention, be improve the specific capacity of anode material for lithium-ion batteries and cyclical stability, by same for the mixed solution of precipitation reagent and hydrogen peroxide nickel, cobalt, manganese, aluminium etc. wherein two or more slaine/solution react, add a certain amount of H 2o 2as oxidant and dispersant, and the calcination process part of material or all at O 3carry out under environmental condition.Wherein, H 2o 2and O 3as oxidizing metal ion, thus improve the stability of material also improves its specific capacity; Meanwhile, H 2o 2as dispersant, reduce the reunion of material, thus the conductivity increasing material, improve the specific capacity of material further.
The invention has the beneficial effects as follows, in the process of the same nickel of mixed solution, cobalt, manganese, aluminium etc. of precipitation reagent and hydrogen peroxide wherein two or more slaine/solution reactions, add H 2o 2, and O is used in heat treatment process 3, can effectively improve material is as the specific capacity of anode material for lithium-ion batteries and cyclical stability.When with nickel, cobalt, manganese, aluminium etc., wherein two or more slaine/solution prepare anode material for lithium-ion batteries, additive H wherein 2o 2cheap and easy to get and environmental protection, the O adopted in heat treatment process 3obtained by ozone generator, with low cost.These two kinds of additives are used to make material has better chemical property, has broad application prospects.
Accompanying drawing explanation
This explanation comprises following accompanying drawing:
Fig. 1 is the building-up process schematic diagram of material.
Embodiment
With reference to Fig. 1, as the preferred embodiment that may be applied to industry
The present invention's nickel, cobalt, manganese, aluminium etc. wherein two or more slaine/solution prepare anode material for lithium-ion batteries, comprise the steps:
With intermediate water by nickel, cobalt, manganese, aluminium etc. wherein two or more slaine/solution mix and precipitation reagent and H 2o 2mixed solution react; Lithium source is added and at O by reacting the product that obtains 3heat-treat under atmosphere, needed for obtaining material.
Concrete case study on implementation 1:
When x=y=z=1/3, with said method synthesis nickel-cobalt-manganese ternary alloy positive electrode--- .
Pass through Co deposited synthesis material presoma.With intermediate water be the nickel nitrate of 1:1:1 by mol ratio, cobalt nitrate and manganese nitrate mix, afterwards by precipitation reagent LiOHH 2o is slowly added drop-wise in nitrate solution.Wherein, at LiOHH 2add a certain amount of hydrogen peroxide in O solution as oxidant and dispersant, add a certain amount of ammoniacal liquor as complexing agent.The temperature of precipitation process controls 45 oc.In this process, the mixed solution of lithium hydroxide, hydrogen peroxide and ammoniacal liquor joins in nitrate solution slowly, regulates the pH value of solution to 10.7 more afterwards, afterwards mother liquor is left standstill 2 to 3 hours with ammoniacal liquor as pH adjusting agent.Finally by suspension filtered, with distilled water repeatedly centrifuge washing until supernatant liquor is in neutral.
Precursor in vacuum drying oven 60 DEG C, dries for 12 hours, by its 450 DEG C of pre-burning 5 hours under ozone condition in tube furnace.By a certain amount of burned in advance with a certain amount of Li 2cO 3mix and grind to form uniform powder, grinding is even further again as dispersant to add ethanol afterwards, dries.Finally, the mixed-powder of oven dry is placed in tube furnace under ozone condition 800 DEG C calcining 15 hours, naturally cooling, obtain material requested.
This method is obtained material is used as anode material for lithium-ion batteries.After tested, the first discharge specific capacity of electrode material is relative to without hydrogen peroxide-ozone treatment electrode material first discharge specific capacity exceeds nearly 65 mAh g -1.Its cyclical stability also has relative raising simultaneously, and electrode material prepared by this method is after 50 circle circulations, and its capability retention exceeds 40% than the material without hydrogen peroxide-ozone treatment.
Concrete case study on implementation 2:
By Co deposited synthesis LiNi 0.3co 0.2mn 0.3al 0.1o 2the presoma Ni of material 0.3co 0.2mn 0.3al 0.1(OH) 2.With intermediate water, the nickelous sulfate of mol ratio 3:2:3:0.5, cobaltous sulfate, manganese sulfate and aluminum sulfate are mixed, afterwards precipitation reagent is slowly added drop-wise in sulfate liquor.Wherein, in precipitation reagent, add a certain amount of hydrogen peroxide as oxidant and dispersant, add a certain amount of ammoniacal liquor as complexing agent, react and carry out at 50 DEG C.Finally regulate the pH value of solution to be 10.3 with ammoniacal liquor as pH adjusting agent again, afterwards mother liquor is left standstill 4 hours.Finally by suspension filtered, with distilled water repeatedly centrifuge washing until supernatant liquor is in neutral.
Precursor is dried, by its 450 DEG C of pre-burning 5 hours under ozone condition in tube furnace, presoma burned in advance and a certain amount of lithium source are mixed and grind to form uniform powder, the powder mixed is placed in tube furnace under ozone condition 800 DEG C calcining 15 hours, naturally cool, obtain material requested.The LiNi obtained by this method 0.3co 0.2mn 0.3al 0.1o 2material is used as anode material for lithium-ion batteries.After tested, the first discharge specific capacity of electrode material is 211.3 mAh g -1.

Claims (5)

1. by nickel, cobalt, manganese, aluminium etc. wherein two or more slaine/solution prepare the method for anode material for lithium-ion batteries:
By wherein two or more slaine/solution reactions such as precipitation reagent and nickel, cobalt, manganese, aluminium, obtain corresponding hydroxide, i.e. the presoma of anode material for lithium-ion batteries; In resulting materials, add lithium source and heat-treat, namely obtaining (0<x+y+z≤1; M:Al, Fe, Zn ...) material.
2. nickel as claimed in claim 1, cobalt, manganese, aluminium etc. wherein two or more slaine/solution prepare the method for precursor of lithium ionic cell positive material:
1. with intermediate water by nickel, cobalt, manganese, aluminium etc. wherein two or more slaine/solution mix;
2. by the same nickel of mixed solution, cobalt, manganese, aluminium etc. of precipitation reagent and hydrogen peroxide wherein two or more slaine/solution react, obtain material precursor---Ni xco ymn zm 1-x-y-z(OH) 2.
3. nickel as claimed in claim 1, cobalt, manganese, aluminium etc. wherein two or more slaine/solution prepare anode material for lithium-ion batteries heat-treating methods:
1. by precipitation reagent and nickel, cobalt, manganese, aluminium etc. wherein two or more slaine/solution reactions obtain material precursor---Ni xco ymn zm 1-x-y-z(OH) 2, gained presoma is heat-treated, heat treatment process part or all at O 3carry out under existence condition.
4. as claimed in claim 2 by nickel, cobalt, manganese, aluminium etc. wherein two or more slaine/solution prepare the method for anode material for lithium-ion batteries, it is characterized in that: described method 2. in, add hydrogen peroxide in precipitation reagent as oxidizing metal ion, also reduce the reunion of material simultaneously as dispersant.
5. as claimed in claim 3 by nickel, cobalt, manganese, aluminium etc. wherein two or more slaine/solution prepare the method for anode material for lithium-ion batteries, it is characterized in that: method 1. in, heat treatment process part or all at O 3carry out under existent condition.
CN201510021393.9A 2015-01-16 2015-01-16 Method of preparing lithium ion battery anode material from two or more metal salts/solutions of nickel, cobalt, manganese, aluminum and the like Pending CN104835956A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105428639A (en) * 2015-11-12 2016-03-23 广东邦普循环科技有限公司 Nickel cobalt lithium manganate positive electrode material and preparation method therefor
CN107256962A (en) * 2017-06-19 2017-10-17 上海纳米技术及应用国家工程研究中心有限公司 The tertiary cathode material nickel cobalt aluminium and preparation method and application of a kind of aluminium foil growth in situ
CN109904443A (en) * 2019-01-17 2019-06-18 浙江工业大学 A kind of preparation method of ternary cathode material of lithium ion battery
CN111446445A (en) * 2020-04-21 2020-07-24 西北工业大学 Plasma treatment method for nickel-based lithium ion positive electrode material precursor
WO2023098169A1 (en) * 2021-11-30 2023-06-08 广东邦普循环科技有限公司 Manganese-rich sodium-ion positive electrode material, preparation method therefor, and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1741302A (en) * 2005-09-15 2006-03-01 河北工业大学 Method for producing anode active material containing lithium, magnesium compound oxide
CN1787258A (en) * 2004-12-07 2006-06-14 深圳市比克电池有限公司 Lithium composite xoide containing manganese cobalt and nickel, its preparation process and application in lithium ion secondary battery thereof
CN1966410A (en) * 2005-11-17 2007-05-23 比亚迪股份有限公司 Preparation method of nickel magnesium cobalt hydroxide
CN101208269A (en) * 2005-11-02 2008-06-25 Agc清美化学股份有限公司 Lithium-containing composite oxide and its production process
CN102709544A (en) * 2012-06-06 2012-10-03 中南大学 Nickel cobalt lithium manganate composite cathode material and preparation method of nickel cobalt lithium manganate composite cathode material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1787258A (en) * 2004-12-07 2006-06-14 深圳市比克电池有限公司 Lithium composite xoide containing manganese cobalt and nickel, its preparation process and application in lithium ion secondary battery thereof
CN1741302A (en) * 2005-09-15 2006-03-01 河北工业大学 Method for producing anode active material containing lithium, magnesium compound oxide
CN101208269A (en) * 2005-11-02 2008-06-25 Agc清美化学股份有限公司 Lithium-containing composite oxide and its production process
CN1966410A (en) * 2005-11-17 2007-05-23 比亚迪股份有限公司 Preparation method of nickel magnesium cobalt hydroxide
CN102709544A (en) * 2012-06-06 2012-10-03 中南大学 Nickel cobalt lithium manganate composite cathode material and preparation method of nickel cobalt lithium manganate composite cathode material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105428639A (en) * 2015-11-12 2016-03-23 广东邦普循环科技有限公司 Nickel cobalt lithium manganate positive electrode material and preparation method therefor
CN105428639B (en) * 2015-11-12 2018-03-02 广东邦普循环科技有限公司 A kind of nickel-cobalt lithium manganate cathode material and preparation method thereof
CN107256962A (en) * 2017-06-19 2017-10-17 上海纳米技术及应用国家工程研究中心有限公司 The tertiary cathode material nickel cobalt aluminium and preparation method and application of a kind of aluminium foil growth in situ
CN109904443A (en) * 2019-01-17 2019-06-18 浙江工业大学 A kind of preparation method of ternary cathode material of lithium ion battery
CN111446445A (en) * 2020-04-21 2020-07-24 西北工业大学 Plasma treatment method for nickel-based lithium ion positive electrode material precursor
WO2023098169A1 (en) * 2021-11-30 2023-06-08 广东邦普循环科技有限公司 Manganese-rich sodium-ion positive electrode material, preparation method therefor, and application thereof

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Application publication date: 20150812