CN101944602A - Preparation method of nano-ternary complex lithium-ion battery cathode material - Google Patents

Preparation method of nano-ternary complex lithium-ion battery cathode material Download PDF

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Publication number
CN101944602A
CN101944602A CN2010102937186A CN201010293718A CN101944602A CN 101944602 A CN101944602 A CN 101944602A CN 2010102937186 A CN2010102937186 A CN 2010102937186A CN 201010293718 A CN201010293718 A CN 201010293718A CN 101944602 A CN101944602 A CN 101944602A
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preparation
ion battery
plate material
potassium ion
plus plate
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赵金鑫
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Irico Group Corp
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Irico Group Corp
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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
    • 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

Abstract

The invention provides a preparation method of a nano-ternary complex lithium-ion battery cathode material, which comprises the following steps: 1) respectively dissolving soluble Li, Ni, Co and Mn compounds into deionized water according to the molar ratio of 1: x: y: z, mixing four kinds of solution, fully stirring and obtaining the uniform mixed solution, wherein x is not less than 0 and not more than 0.5, y is not less than 0.2 and not more than 0.6, z is not less than 0 and not more than 0.5, and x plus y plus z is equal to 1; 2) adding citric acid into the mixed solution as a metal ion chelating agent; and 3) transferring the mixed solution into a water bath pot for heating, carrying out full reaction, forming sol, carrying out vacuum drying on the obtained sol, then carrying out high-temperature sintering in air and obtaining the cathode material with the primary particle diameter of below 100nm and the molecular formula of LiNixCoyMnzO2. Compared with the prior art, the preparation method can prepare the LiNixCoyMnzO2 ternary material with primary particles of below 100nm by adopting the sol-gel method.

Description

A kind of preparation method of nanometer ternary compound potassium ion battery plus plate material
Technical field
The invention belongs to energy and material preparation technology field, relate to a kind of preparation method of nanometer ternary compound potassium ion battery plus plate material.
Background technology
Advantage such as stratiform ternary material Li-Ni-Co-Mn-O has that height ratio capacity, cost are lower, stable cycle performance, fail safe are good, and can effectively remedy LiCoO 2, LiNiO 2, LiMnO 2Deficiency separately, so the exploitation of ternary material becomes the research focus in positive electrode field.The process route of current synthesis of ternary system is to adopt high temperature solid-state method, by mechanical means refinement mixing after high temperature sintering obtains such positive electrode, high temperature solid-state method is simple because of equipment and technology, it is most widely used general in field of material preparation to be easy to industrialization, but the high temperature solid-state method of mechanical mixture has following shortcoming: the mechanical mixture uniformity is limited, is unfavorable for that effective element mixes the solid solution that forms the character homogeneous in sintering process; Influence the material property function, particle size distribution is not concentrated, and easily introduces impurity in mechanical refinement and the mixed process, needs higher reaction temperature and longer reaction time energy consumption bigger for realizing that effective element fully spreads.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of nanometer ternary compound potassium ion battery plus plate material.
To achieve these goals, the present invention adopts following technical scheme:
A kind of preparation method of nanometer ternary compound potassium ion battery plus plate material, may further comprise the steps: 1) with solubility Li, Ni, Co, Mn compound by 1: the mol ratio of x: y: z is dissolved in the deionized water respectively, four kinds of solution are mixed also fully stirring to get a uniform mixture, wherein, 0≤x≤0.5,0.2≤y≤0.6,0≤z≤0.5, x+y+z=1; 2) in mixed solution, add citric acid as metal ion chelation agent; 3) will be described mixed solution move in the water-bath and heat, fully react and form colloidal sol, gained colloidal sol is LiNi through promptly obtaining molecular formula through high temperature sintering after the vacuumize in air xCo yMn zO 2Positive electrode.
Solubility Li compound is that lithium acetate, lithium nitrate, lithium sulfate, lithium halide are a kind of.
Solubility Ni compound is a kind of in nickel nitrate, nickel acetate, the nickelous sulfate; Solubility Co compound is a kind of in cobalt nitrate, cobalt oxalate, the cobalt acetate; Soluble M n compound is a kind of in manganese nitrate, the manganese acetate.
The consumption of described metal ion chelation agent citric acid is 2-5 a times of all metal ions amount of substance summation in the reactant.
The heating-up temperature of described mixed solution in water-bath is 85 ℃-100 ℃.
The baking temperature of described colloidal sol in vacuum drying chamber is 100 ℃-150 ℃.
The sintering temperature of described desciccate is 750 ℃-900 ℃, and sintering time was greater than 6 hours.
The mol ratio of Li, Ni, Co, Mn element is 1: 0.2: 0.5 in described solubility Li, Ni, Co, the Mn compound: 0.3.
The mol ratio of Li, Ni, Co, Mn element is 1: 0.2: 0.6 in described solubility Li, Ni, Co, the Mn compound: 0.2.
The mol ratio of Li, Ni, Co, Mn element is 1: 0.4: 0.2 in described solubility Li, Ni, Co, the Mn compound: 0.4.
Compared with prior art, the present invention has the following advantages: adopt Prepared by Sol Gel Method to go out the LiNi of primary particle below 100nm xCo yMn zO 2Ternary material, this process adopts the method for liquid-phase mixing reactant, the mixing that realizes molecular level between each element has avoided the active ingredient that ball mill mixing causes in the solid phase synthesis process to mix impurity inhomogeneous and that ball milling is introduced, the gained sample need not reprocessing can obtain the nano particle that particle size distribution is concentrated, LiNi xCo yMn zO 2The consistency performance of material is increased dramatically.
Description of drawings
Fig. 1 is with the SEM of embodiment 1 gained sample (scanning electron microscopy) image.
Embodiment
Below by specific embodiment the present invention is done detailed description, following embodiment only is used to illustrate the present invention, but and is not used in and limits practical range of the present invention.
Embodiment 1:
Respectively lithium nitrate, nickel nitrate, cobalt nitrate, manganese nitrate are dissolved in and form homogeneous phase solution in the deionized water, Li: Ni: Co wherein: the Mn mol ratio is 1: 0.2: 0.5: 0.3, above-mentioned solution is mixed the citric acid of 3 times of back adding all metal ions amount of substances as metal ion chelation agent and abundant the stirring, mixed solution is moved in the water-bath 95 ℃ of heated at constant temperature until forming the colloidal sol shape, presoma 850 ℃ of sintering in air of gained colloidal sol gained after 120 ℃ of vacuumize were promptly obtained the α-NaFeO of primary particle particle diameter below 100nm in 10 hours 2Type LiNi 0.2Co 0.5Mn 0.3O 2Positive electrode.
See also that this process of employing shown in Figure 1 prepares sample and has that particle size distribution is concentrated, the primary particle particle diameter is less than the characteristics of 100nm.It is to obtain the ball-milling treatment technology that satisfied particle size distribution is taked that this process has effectively avoided adopting high temperature solid-state method synthesis of ternary material, avoids in the mechanical milling process introducing to physical damage and the impurity of crystal.
Embodiment 2:
Respectively lithium nitrate, nickel acetate, cobalt oxalate, manganese nitrate are dissolved in and form homogeneous phase solution in the deionized water, Li: Ni: Co wherein: the Mn mol ratio is 1: 0.2: 0.6: 0.2, above-mentioned solution is mixed the citric acid of 5 times of back adding all metal ions amount of substances as metal ion chelation agent and abundant the stirring, mixed solution is moved in the water-bath 85 ℃ of heated at constant temperature until forming the colloidal sol shape, presoma 750 ℃ of sintering in air of gained colloidal sol gained after 100 ℃ of vacuumize gained dryings were promptly obtained the α-NaFeO of primary particle particle diameter below 100nm in 22 hours 2Type LiNi 0.2Co 0.6Mn 0.2O 2Positive electrode.
Embodiment 3:
Respectively lithium nitrate, nickelous sulfate, cobalt oxalate, manganese nitrate are dissolved in and form homogeneous phase solution in the deionized water, Li: Ni: Co wherein: the Mn mol ratio is 1: 0.4: 0.2: 0.4, above-mentioned solution is mixed the citric acid of 2 times of back adding all metal ions amount of substances as metal ion chelation agent and abundant the stirring, mixed solution is moved in the water-bath 90 ℃ of heated at constant temperature until forming the colloidal sol shape, presoma 900 ℃ of sintering in air of gained colloidal sol gained after 100 ℃ of vacuumize gained dryings were promptly obtained the α-NaFeO of primary particle particle diameter below 100nm in 8 hours 2Type LiNi 0.4Co 0.2Mn 0.4O 2Positive electrode.
Embodiment 4:
Respectively lithium sulfate, nickelous sulfate, cobalt oxalate are dissolved in and form homogeneous phase solution in the deionized water, Li: Ni wherein: the Co mol ratio is 1: 0.5: 0.5, above-mentioned solution is mixed the citric acid of 2 times of back adding all metal ions amount of substances as metal ion chelation agent and abundant the stirring, mixed solution is moved in the water-bath 95 ℃ of heated at constant temperature until forming the colloidal sol shape, presoma 800 ℃ of sintering in air of gained colloidal sol gained after 150 ℃ of vacuumize gained dryings were promptly obtained the α-NaFeO of primary particle particle diameter below 100nm in 10 hours 2Type LiNi 0.5Co 0.5O 2Positive electrode.
Embodiment 5:
Respectively lithium acetate, manganese nitrate, cobalt oxalate are dissolved in and form homogeneous phase solution in the deionized water, Li: Mn wherein: the Co mol ratio is 1: 0.5: 0.5, above-mentioned solution is mixed the citric acid of 3 times of back adding all metal ions amount of substances as metal ion chelation agent and abundant the stirring, mixed solution is moved in the water-bath 100 ℃ of heated at constant temperature until forming the colloidal sol shape, presoma 850 ℃ of sintering in air of gained colloidal sol gained after 120 ℃ of vacuumize gained dryings were promptly obtained the α-NaFeO of primary particle particle diameter below 100nm in 10 hours 2Type LiMn 0.5Co 0.5O 2Positive electrode.

Claims (10)

1. the preparation method of a nanometer ternary compound potassium ion battery plus plate material is characterized in that, may further comprise the steps:
1) with solubility Li, Ni, Co, Mn compound by 1: the mol ratio of x: y: z is dissolved in respectively in the deionized water, four kinds of solution are mixed and fully stir getting a uniform mixture, wherein, 0≤x≤0.5,0.2≤y≤0.6,0≤z≤0.5, x+y+z=1;
2) in mixed solution, add citric acid as metal ion chelation agent;
3) will be described mixed solution move in the water-bath and heat, fully react and form colloidal sol, gained colloidal sol is LiNi through promptly obtaining molecular formula through high temperature sintering after the vacuumize in air xCo yMn zO 2Positive electrode.
2. a kind of according to claim 1 preparation method of nanometer ternary compound potassium ion battery plus plate material is characterized in that: solubility Li compound is that lithium acetate, lithium nitrate, lithium sulfate, lithium halide are a kind of.
3. a kind of according to claim 1 preparation method of nanometer ternary compound potassium ion battery plus plate material, it is characterized in that: solubility Ni compound is a kind of in nickel nitrate, nickel acetate, the nickelous sulfate; Solubility Co compound is a kind of in cobalt nitrate, cobalt oxalate, the cobalt acetate; Soluble M n compound is a kind of in manganese nitrate, the manganese acetate.
4. a kind of according to claim 1 preparation method of nanometer ternary compound potassium ion battery plus plate material is characterized in that: the consumption of described metal ion chelation agent citric acid be all metal ions amount of substance summation in the reactant 2-5 doubly.
5. a kind of according to claim 1 preparation method of nanometer ternary compound potassium ion battery plus plate material, it is characterized in that: the heating-up temperature of described mixed solution in water-bath is 85 ℃-100 ℃.
6. a kind of according to claim 1 preparation method of nanometer ternary compound potassium ion battery plus plate material, it is characterized in that: the baking temperature of described colloidal sol in vacuum drying chamber is 100 ℃-150 ℃.
7. a kind of according to claim 1 preparation method of nanometer ternary compound potassium ion battery plus plate material, it is characterized in that: the sintering temperature of described desciccate is 750 ℃-900 ℃, and sintering time was greater than 6 hours.
8. a kind of according to claim 1 preparation method of nanometer ternary compound potassium ion battery plus plate material, it is characterized in that: the mol ratio of Li, Ni, Co, Mn element is 1: 0.2: 0.5 in described solubility Li, Ni, Co, the Mn compound: 0.3.
9. a kind of according to claim 1 preparation method of nanometer ternary compound potassium ion battery plus plate material, it is characterized in that: the mol ratio of Li, Ni, Co, Mn element is 1: 0.2: 0.6 in described solubility Li, Ni, Co, the Mn compound: 0.2.
10. a kind of according to claim 1 preparation method of nanometer ternary compound potassium ion battery plus plate material, it is characterized in that: the mol ratio of Li, Ni, Co, Mn element is 1: 0.4: 0.2 in described solubility Li, Ni, Co, the Mn compound: 0.4.
CN2010102937186A 2010-09-27 2010-09-27 Preparation method of nano-ternary complex lithium-ion battery cathode material Pending CN101944602A (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102263238A (en) * 2011-06-13 2011-11-30 常熟理工学院 Lithium nickel cobalt manganese oxide and preparation method thereof
CN102694164A (en) * 2012-06-08 2012-09-26 南开大学 Lithium oxide-rich cathode material with nitrogen or carbon-doped surface and preparation method for cathode material
CN102709568A (en) * 2012-06-25 2012-10-03 天津工业大学 Preparation method for nickel cobalt lithium manganate LiNixConMn1-x-yO2 of anode material of lithium ion battery
CN103000877A (en) * 2012-12-14 2013-03-27 彩虹集团公司 Composite lithium ion anode material based on lithium-nickel-cobalt-manganese oxide and preparation method thereof
CN103531763A (en) * 2013-10-24 2014-01-22 广东邦普循环科技股份有限公司 Preparation method of nickel cobalt lithium manganate
CN104009239A (en) * 2013-12-16 2014-08-27 青岛乾运高科新材料股份有限公司 Nano carbon doped manganese-based solid solution anode material and preparation method thereof
CN104253273A (en) * 2013-06-28 2014-12-31 江南大学 Anion/cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof
CN105118986A (en) * 2015-08-28 2015-12-02 洛阳理工学院 Preparation method for nickel-cobalt lithium manganate serving as high-performance lithium ion battery positive electrode material
CN105140470A (en) * 2015-07-10 2015-12-09 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of carbon nanotube @ ternary @ silver composite material of lithium-ion battery
CN105680034A (en) * 2016-04-22 2016-06-15 柳州凯通新材料科技有限公司 Synthesis process of nickel-cobalt lithium manganate anode material
CN105680038A (en) * 2016-04-22 2016-06-15 柳州凯通新材料科技有限公司 Method for synthesizing LiNixCoyMn1-x-yO2 anode material with sol-gel process
CN106935799A (en) * 2017-03-17 2017-07-07 成都新柯力化工科技有限公司 The nickle cobalt lithium manganate ternary positive plate of lithium battery and preparation method of a kind of stabilization
CN109326778A (en) * 2018-09-11 2019-02-12 武汉理工大学 A kind of tertiary cathode material and preparation method thereof of nickel acid lanthanum cladding
CN113328087A (en) * 2021-05-17 2021-08-31 宜宾锂宝新材料有限公司 Lithium ion battery anode material and preparation method thereof

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CN1597535A (en) * 2004-08-06 2005-03-23 哈尔滨工业大学 Preparation of potassium lithium niobate nanometer powder using citric acid gelification method
CN1821080A (en) * 2006-03-13 2006-08-23 吉林大学 Lithium ion secondary cell positive pole material and its preparing method

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CN1597535A (en) * 2004-08-06 2005-03-23 哈尔滨工业大学 Preparation of potassium lithium niobate nanometer powder using citric acid gelification method
CN1821080A (en) * 2006-03-13 2006-08-23 吉林大学 Lithium ion secondary cell positive pole material and its preparing method

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102263238A (en) * 2011-06-13 2011-11-30 常熟理工学院 Lithium nickel cobalt manganese oxide and preparation method thereof
CN102694164A (en) * 2012-06-08 2012-09-26 南开大学 Lithium oxide-rich cathode material with nitrogen or carbon-doped surface and preparation method for cathode material
CN102709568A (en) * 2012-06-25 2012-10-03 天津工业大学 Preparation method for nickel cobalt lithium manganate LiNixConMn1-x-yO2 of anode material of lithium ion battery
CN103000877A (en) * 2012-12-14 2013-03-27 彩虹集团公司 Composite lithium ion anode material based on lithium-nickel-cobalt-manganese oxide and preparation method thereof
CN104253273A (en) * 2013-06-28 2014-12-31 江南大学 Anion/cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof
CN103531763B (en) * 2013-10-24 2015-12-02 广东邦普循环科技有限公司 A kind of method preparing nickle cobalt lithium manganate
CN103531763A (en) * 2013-10-24 2014-01-22 广东邦普循环科技股份有限公司 Preparation method of nickel cobalt lithium manganate
CN104009239A (en) * 2013-12-16 2014-08-27 青岛乾运高科新材料股份有限公司 Nano carbon doped manganese-based solid solution anode material and preparation method thereof
CN105140470A (en) * 2015-07-10 2015-12-09 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of carbon nanotube @ ternary @ silver composite material of lithium-ion battery
CN105140470B (en) * 2015-07-10 2017-05-17 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of carbon nanotube @ ternary @ silver composite material of lithium-ion battery
CN105118986A (en) * 2015-08-28 2015-12-02 洛阳理工学院 Preparation method for nickel-cobalt lithium manganate serving as high-performance lithium ion battery positive electrode material
CN105680034A (en) * 2016-04-22 2016-06-15 柳州凯通新材料科技有限公司 Synthesis process of nickel-cobalt lithium manganate anode material
CN105680038A (en) * 2016-04-22 2016-06-15 柳州凯通新材料科技有限公司 Method for synthesizing LiNixCoyMn1-x-yO2 anode material with sol-gel process
CN106935799A (en) * 2017-03-17 2017-07-07 成都新柯力化工科技有限公司 The nickle cobalt lithium manganate ternary positive plate of lithium battery and preparation method of a kind of stabilization
CN106935799B (en) * 2017-03-17 2018-10-12 江苏润寅石墨烯科技有限公司 A kind of the nickle cobalt lithium manganate ternary positive plate of lithium battery and preparation method of stabilization
CN109326778A (en) * 2018-09-11 2019-02-12 武汉理工大学 A kind of tertiary cathode material and preparation method thereof of nickel acid lanthanum cladding
CN109326778B (en) * 2018-09-11 2021-08-24 武汉理工大学 Lanthanum nickelate coated ternary cathode material and preparation method thereof
CN113328087A (en) * 2021-05-17 2021-08-31 宜宾锂宝新材料有限公司 Lithium ion battery anode material and preparation method thereof

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