CN102544480A - Method for preparing nanometer ternary composite lithium cell cathode material - Google Patents

Method for preparing nanometer ternary composite lithium cell cathode material Download PDF

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CN102544480A
CN102544480A CN2011104567116A CN201110456711A CN102544480A CN 102544480 A CN102544480 A CN 102544480A CN 2011104567116 A CN2011104567116 A CN 2011104567116A CN 201110456711 A CN201110456711 A CN 201110456711A CN 102544480 A CN102544480 A CN 102544480A
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ternary composite
positive electrode
preparation
ion battery
lithium ion
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王少卿
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Irico Group Corp
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Irico Group Corp
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a method for preparing a nanometer ternary composite lithium cell cathode material. The method comprises the following steps of: preparing a precursor of a nanometer-level (the particle size is below 100nm) by a sol-gel method mainly, and carrying out quick sintering synthesis through microwaves, wherein each reaction raw material can realize molecular-level mixing of elements through the sol-gel method so that a problem of non-uniform mixing in a solid phase method is avoided; and simultaneously, materials are directly heated through microwave sintering so that the material is heated uniformly, particles of products are more uniform and consistent, phases are uniform, the degree of crystallization is better, and the electric performance quality of products can be improved.

Description

A kind of preparation method of nanometer ternary composite lithium ion battery positive electrode
Technical field
The invention belongs to technical field of lithium ion, relate to a kind of preparation method of nanometer ternary composite lithium ion battery positive electrode.
Background technology
In lithium ion battery, positive electrode is its most important component, also is the key of decision lithium ion battery performance.Under the prerequisite of same capacity performance, improve the volume of battery energy density, will improve the loading of cell active materials unit volume.And 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, LiMn 2O 4Deficiency separately, so the exploitation of ternary material becomes the positive electrode hot research fields.
Traditional preparation method generally through mechanical mixing with two kinds of material mixing together; Method through composite material reaches and reduces cost; Improve peace and fill safety and thermal stability, but this simple physics method of mixing tends to have influence on material property, or adopt high temperature solid-state method; Through mechanical refinement mixing after high temperature sintering obtains such positive electrode; But its drawback is to be unfavorable for that effective element mixes the solid solution that in sintering process, forms the character homogeneous, and material particle size is difficult to evenly, and introduces impurity easily.Meanwhile, it is synthetic through the long sintering of high temperature sintering furnace mostly current ternary material is, raw material is heated inhomogeneously in the sintering process, and thing phase purity is limited to, and power consumption is huge, and cost is higher.
Summary of the invention
In order to solve above-mentioned existing problem; The present invention provides a kind of preparation method of nanometer ternary composite lithium ion battery positive electrode; Solved solid phase method synthetic in material be heated inhomogeneously, the drawback of product cut size consistency difference obtains the uniform nanoscale tertiary cathode material of degree of crystallinity.
The present invention realizes through following technical scheme:
A kind of preparation method of nanometer ternary composite lithium ion battery positive electrode may further comprise the steps:
1) respectively with the compound of solubility Li, Ni, Co, Mn by 1: the mol ratio of x: y: z is dissolved in deionized water, fully stir to get a uniform mixture, wherein, 0≤x≤0.4,0.1≤y≤0.5,0≤z≤0.5, x+y+z=1;
2) in mixed solution, add the metal ion intercalating agent, and be heated to 80～100 ℃, form sol precursor after fully reacting 1～2h;
Under vacuum condition, gained precursor sol body and function microwave heat is heated to 40～60 ℃, insulation 1～2h obtains presoma;
3) the gained presoma is placed carry out sintering in the microwave oven, adjusting power is 2～4kw, and sintering time is 4～6h, promptly gets thing nanometer ternary composite positive pole LiNi uniformly mutually xCo yMn zO 2
The metal ion intercalating agent of described adding is 2～8 times of Li amount of substance.
Described solubility Li compound is that lithium nitrate, lithium sulfate, lithium acetate, lithium halide are a kind of.
Described metal-chelator is a kind of of citric acid, tartaric acid, grape credit acid.
Described solubility Ni compound is a kind of in nickel nitrate, the nickel acetate; 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.
After adding the metal ion intercalating agent in the described mixed solution, under water bath condition, be heated to 80～100 ℃.
The heating of described sol precursor is to heat in the microwave vacuum dryer.
Described vacuum condition is that vacuum degree is 10 -5Pa.
Compared with prior art, the present invention has following beneficial technical effects:
The preparation method of nanometer ternary composite lithium ion battery positive electrode provided by the invention, this method mainly go out the presoma of nanoscale (particle diameter is below 100nm) through Prepared by Sol Gel Method, carry out Fast Sintering through microwave again and synthesize; Sol-gal process technology can make each reaction raw materials realize the mixing of molecular level between element, avoids mixing in the solid phase method uneven problem.Through microwave sintering, material is directly heated simultaneously, make material be heated evenly, the product particle is uniformity more, and thing is mutually even, and degree of crystallinity is better, can promote product electrical property quality.
Description of drawings
The SEM shape appearance figure of the nanometer ternary composite lithium ion battery positive electrode that Fig. 1 synthesizes for the present invention.
Embodiment
The present invention provides a kind of preparation method of nanometer ternary composite lithium ion battery positive electrode, and this method mainly goes out nano level presoma through Prepared by Sol Gel Method, carries out Fast Sintering through microwave again and synthesizes.Below in conjunction with concrete embodiment the present invention is done further detailed description, said is to explanation of the present invention rather than qualification.
Embodiment 1
The preparation method of nanometer ternary composite lithium ion battery positive electrode may further comprise the steps:
1) taking by weighing mol ratio is 1: 0.1: 0.5: 0.4 lithium nitrate, nickel nitrate, cobalt nitrate, manganese nitrate raw material, be dissolved in respectively in the deionized water, and then four kinds of solution are mixed, fully stirring gets a uniform mixture.
2) in mixed solution, add 3 times of citric acids and make intercalating agent to the amount of above-mentioned metal ion species, and in water-bath 80 ℃ heat, form sol precursor after fully reacting 2h, with gained sol precursor material in microwave vacuum dryer in 1 * 10 -5The following 40 ℃ of dry 2h of Pa vacuum degree, promptly obtaining particle diameter is the presoma below the 100nm.
3) the gained presoma is placed in the microwave agglomerating furnace, 2kw sintering 6h, obtaining the even mutually molecular formula of thing is LiNi 0.1Co 0.5Mn 0.4O 2Nanometer ternary composite positive pole.The gained sample topography is as shown in Figure 1.
Embodiment 2
The preparation method of nanometer ternary composite lithium ion battery positive electrode may further comprise the steps:
1) taking by weighing mol ratio is 1: 0.4: 0.1: 0.5 lithium nitrate, nickel nitrate, cobalt nitrate, manganese nitrate raw material, be dissolved in respectively in the deionized water, and then four kinds of solution are mixed, fully stirring gets a uniform mixture.
2) in mixed solution, add 2 times of citric acids and make intercalating agent to the amount of above-mentioned metal ion species; And in water-bath 95 ℃ heat; Fully forming sol precursor behind the reaction 1.5h, is 10 in vacuum degree with gained sol precursor material in microwave vacuum dryer -5Under the Pa, 50 ℃ of dry 1h, promptly obtain particle diameter and be the presoma below the 100nm.
3) the gained presoma is placed in the microwave agglomerating furnace, 3kw sintering 5h, obtaining the even mutually molecular formula of thing is LiNi 0.4Co 0.1Mn 0.5O 2Nanometer ternary composite positive pole.
Embodiment 3
The preparation method of nanometer ternary composite lithium ion battery positive electrode may further comprise the steps:
1) taking by weighing mol ratio is 1: 0.2: 0.5: 0.3 lithium nitrate, nickel nitrate, cobalt nitrate, manganese nitrate raw material, be dissolved in respectively in the deionized water, and then four kinds of solution are mixed, fully stirring gets a uniform mixture.
2) in mixed solution, add 4 times of citric acids and make intercalating agent to the amount of above-mentioned metal ion species; And in water-bath 100 ℃ heat; Fully form sol precursor behind the reaction 1h, (vacuum degree is 10 in 60 ℃ of dry 1h in microwave vacuum dryer with gained sol precursor material -5Pa), promptly obtaining particle diameter is the presoma below the 100nm.
3) the gained presoma is placed in the microwave agglomerating furnace, 4kw sintering 4h, obtaining the even mutually molecular formula of thing is LiNi 0.2Co 0.5Mn 0.3O 2Nanometer ternary composite positive pole.
Embodiment 4
The preparation method of nanometer ternary composite lithium ion battery positive electrode may further comprise the steps:
1) taking by weighing mol ratio is 1: 0.3: 0.4: 0.3 lithium nitrate, nickel nitrate, cobalt nitrate, manganese nitrate raw material, be dissolved in respectively in the deionized water, and then four kinds of solution are mixed, fully stirring gets a uniform mixture.
2) in mixed solution, add 3 times of citric acids and make intercalating agent to the amount of above-mentioned metal ion species; And in water-bath 90 ℃ heat; Fully form sol precursor behind the reaction 1h, (vacuum degree is 10 in 60 ℃ of dry 1h in microwave vacuum dryer with gained sol precursor material -5Pa), promptly obtaining particle diameter is the presoma below the 100nm.
3) the gained presoma is placed in the microwave agglomerating furnace, 3kw sintering 5h, obtaining the even mutually molecular formula of thing is LiNi 0.3Co 0.4Mn 0.3O 2Nanometer ternary composite positive pole.
Embodiment 5
The preparation method of nanometer ternary composite lithium ion battery positive electrode may further comprise the steps:
1) taking by weighing mol ratio is 1: 0.3: 0.4: 0.3 lithium sulfate, nickel acetate, cobalt oxalate, manganese acetate raw material, be dissolved in respectively in the deionized water, and then four kinds of solution are mixed, fully stirring gets a uniform mixture.
2) in mixed solution, add 2.5 times of tartaric acid and make intercalating agent to the amount of above-mentioned metal ion species; And in water-bath 90 ℃ heat; Fully form sol precursor behind the reaction 1h, (vacuum degree is 10 in 60 ℃ of dry 1h in microwave vacuum dryer with gained sol precursor material -5Pa), promptly obtaining particle diameter is the presoma below the 100nm.
3) the gained presoma is placed in the microwave agglomerating furnace, 3kw sintering 5h, obtaining the even mutually molecular formula of thing is LiNi 0.3Co 0.4Mn 0.3O 2Nanometer ternary composite positive pole.
Embodiment 6
The preparation method of nanometer ternary composite lithium ion battery positive electrode may further comprise the steps:
1) taking by weighing mol ratio is 1: 0.3: 0.5: 0.2 lithium acetate, nickel acetate, cobalt acetate, manganese acetate raw material, be dissolved in respectively in the deionized water, and then four kinds of solution are mixed, fully stirring gets a uniform mixture.
2) in mixed solution, add 3 times of citric acids and make intercalating agent to the amount of above-mentioned metal ion species; And in water-bath 100 ℃ heat; Fully form sol precursor behind the reaction 1.5h, (vacuum degree is 10 in 55 ℃ of dry 1.2h in microwave vacuum dryer with gained sol precursor material -5Pa), promptly obtaining particle diameter is the presoma below the 100nm.
3) the gained presoma is placed in the microwave agglomerating furnace, 4kw sintering 4h, obtaining the even mutually molecular formula of thing is LiNi 0.3Co 0.5Mn 0.2O 2Nanometer ternary composite positive pole.
Embodiment 7
The preparation method of nanometer ternary composite lithium ion battery positive electrode may further comprise the steps:
1) taking by weighing mol ratio is 1: 0.4: 0.1: 0.5 lithium fluoride, nickel nitrate, cobalt oxalate, manganese nitrate raw material, be dissolved in respectively in the deionized water, and then four kinds of solution are mixed, fully stirring gets a uniform mixture.
2) in mixed solution, add 3 times of citric acids and make intercalating agent to the amount of above-mentioned metal ion species; And in water-bath 90 ℃ heat; Fully form sol precursor behind the reaction 1h, (vacuum degree is 10 in 60 ℃ of dry 1h in microwave vacuum dryer with gained sol precursor material -5Pa), promptly obtaining particle diameter is the presoma below the 100nm.
3) the gained presoma is placed in the microwave agglomerating furnace, 3kw sintering 5h, obtaining the even mutually molecular formula of thing is LiNi 0.4Co 0.1Mn 0.5O 2Nanometer ternary composite positive pole.
Embodiment 8
The preparation method of nanometer ternary composite lithium ion battery positive electrode may further comprise the steps:
1) taking by weighing mol ratio is 1: 0.2: 0.3: 0.2 lithium chloride, nickel acetate, cobalt nitrate, manganese nitrate raw material, be dissolved in respectively in the deionized water, and then four kinds of solution are mixed, fully stirring gets a uniform mixture.
2) in mixed solution, add 3 times of citric acids and make intercalating agent to the amount of above-mentioned metal ion species; And in water-bath 85 ℃ heat; Fully form sol precursor behind the reaction 1.5h, (vacuum degree is 10 in 50 ℃ of dry 2h in microwave vacuum dryer with gained sol precursor material -5Pa), promptly obtaining particle diameter is the presoma below the 100nm.
3) the gained presoma is placed in the microwave agglomerating furnace, 3.5kw sintering 4.5h, obtaining the even mutually molecular formula of thing is LiNi 0.2Co 0.3Mn 0.2O 2Nanometer ternary composite positive pole.

Claims (8)

1. the preparation method of a nanometer ternary composite lithium ion battery positive electrode is characterized in that, may further comprise the steps:
1) respectively with the compound of solubility Li, Ni, Co, Mn by 1: the mol ratio of x: y: z is dissolved in deionized water, fully stir to get a uniform mixture, wherein, 0≤x≤0.4,0.1≤y≤0.5,0≤z≤0.5, x+y+z=1;
2) in mixed solution, add the metal ion intercalating agent, and be heated to 80～100 ℃, form sol precursor after fully reacting 1～2h;
Under vacuum condition, gained precursor sol body and function microwave heat is heated to 40～60 ℃, insulation 1～2h obtains presoma;
3) the gained presoma is placed carry out sintering in the microwave oven, adjusting power is 2～4kw, and sintering time is 4～6h, promptly gets thing nanometer ternary composite positive pole LiNi uniformly mutually xCo yMn zO 2
2. the preparation method of nanometer ternary composite lithium ion battery positive electrode as claimed in claim 1 is characterized in that, the metal ion intercalating agent of described adding is 2～8 times of Li amount of substance.
3. the preparation method of nanometer ternary composite lithium ion battery positive electrode as claimed in claim 1 is characterized in that, described solubility Li compound is that lithium nitrate, lithium sulfate, lithium acetate, lithium halide are a kind of.
4. the preparation method of nanometer ternary composite lithium ion battery positive electrode as claimed in claim 1 is characterized in that, described metal-chelator is a kind of of citric acid, tartaric acid, grape credit acid.
5. the preparation method of nanometer ternary composite lithium ion battery positive electrode as claimed in claim 1 is characterized in that described solubility Ni compound is a kind of in nickel nitrate, the nickel acetate; 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.
6. the preparation method of nanometer ternary composite lithium ion battery positive electrode as claimed in claim 1 is characterized in that, behind the adding metal ion intercalating agent, under water bath condition, is heated to 80～100 ℃ in the described mixed solution.
7. the preparation method of nanometer ternary composite lithium ion battery positive electrode as claimed in claim 1 is characterized in that the heating of described sol precursor is to heat in the microwave vacuum dryer.
8. the preparation method of nanometer ternary composite lithium ion battery positive electrode as claimed in claim 1 is characterized in that, described vacuum condition is that vacuum degree is 10 -5Pa.
CN2011104567116A 2011-12-26 2011-12-26 Method for preparing nanometer ternary composite lithium cell cathode material Pending CN102544480A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103811747A (en) * 2014-03-04 2014-05-21 广东邦普循环科技有限公司 Power-type nickel cobalt manganese acid lithium material as well as preparation method and application thereof
CN105098175A (en) * 2015-08-07 2015-11-25 湖北师范学院 Layered ternary cathode material of lithium ion battery and microwave preparation method of layered ternary cathode material
CN114524471A (en) * 2022-04-22 2022-05-24 宜宾锂宝新材料有限公司 Low-residual-alkali high-nickel ternary cathode material, and preparation method and application thereof

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CN1907844A (en) * 2006-08-11 2007-02-07 广州市鹏辉电池有限公司 High density ultrafine composite ferric lithium phosphate anode material and preparation method
CN101651205A (en) * 2009-08-21 2010-02-17 常熟理工学院 Method for preparing lithium vanadium phosphate as lithium ion battery anode material

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103811747A (en) * 2014-03-04 2014-05-21 广东邦普循环科技有限公司 Power-type nickel cobalt manganese acid lithium material as well as preparation method and application thereof
CN103811747B (en) * 2014-03-04 2016-01-20 广东邦普循环科技有限公司 A kind of power type nickel-cobalt lithium manganate material and its preparation method and application
CN105098175A (en) * 2015-08-07 2015-11-25 湖北师范学院 Layered ternary cathode material of lithium ion battery and microwave preparation method of layered ternary cathode material
CN114524471A (en) * 2022-04-22 2022-05-24 宜宾锂宝新材料有限公司 Low-residual-alkali high-nickel ternary cathode material, and preparation method and application thereof

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Application publication date: 20120704