CN104201334A - Lithium-rich manganese-based anode material for lithium ion battery and preparation method - Google Patents
Lithium-rich manganese-based anode material for lithium ion battery and preparation method Download PDFInfo
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- CN104201334A CN104201334A CN201410384411.5A CN201410384411A CN104201334A CN 104201334 A CN104201334 A CN 104201334A CN 201410384411 A CN201410384411 A CN 201410384411A CN 104201334 A CN104201334 A CN 104201334A
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- lithium
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- based anode
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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
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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
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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
- H01M4/52—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
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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 discloses a lithium-rich manganese-based anode material for a lithium ion battery, and a preparation method. The preparation process comprises the following steps: (1) metal lithium salt, nickel salt, manganese salt and cobalt salt are dissolved in deionized water and mixed to form a transparent solution, sucrose is added into the transparent solution, the solution is agitated to be transparent and then is heated, agitation is performed continuously for evaporation, water in the solution is removed, so that sol is formed firstly, and gel is obtained finally; (2) the gel is subjected to primary calcination at 500 DEG C-550 DEG C for 2h-4h to remove organic ingredients, and then the gel subjected to primary calcination is subjected to secondary calcination at 800 DEG C-900 DEG C for 15h-20h after being ground, the preparation process is greatly simplified, the temperature, the pH value, the feeding speed and the like of a co-precipitation system are not required to be controlled precisely, the contact between primary particles is improved efficiently, and the rate capability of the material is improved.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries field, be specifically related to lithium-rich manganese-based anode material for lithium-ion batteries and preparation method.
Background technology
Lithium ion battery is widely used at present on mobile phone, video camera, notebook computer, portable electronics etc.Compared with traditional secondary cell, lithium ion battery has the advantages such as platform voltage high (approximately 3.2～3.7V), energy density are high, memory-less effect.It is positive electrode that the lithium ion battery that early stage commercialization is produced mainly adopts LiCoO2, LiCoO2 has higher capacity and good stability, but this positive electrode exists in performance, problem economically, on environment, needs people to develop new positive electrode system and meets the demand of people to energy-storage battery energy density, power density, fail safe, low cost etc.Hzuku and Makimura etc. disclose LiMn1/3Ni1/3Co1/3O2 at document " for the Layered Lithium ion insert type positive electrode LiCo1/3Ni1/3Mn1/3O2 of lithium ion battery " (Chemistry Letters7 (2001) 642-643), find manganese, nickel, effectively combination of cobalt, in reducing costs, also can form the layer structure of ternary, wherein manganese element is+4 valencys, play the effect of charge compensation, nickel is+divalent, be main redox reaction active material, and cobalt is+3 valencys.But its capacity is limited, under 2.5～4.6V, discharge capacity is about 200mAh/g.
In order to improve energy density and the power density of battery, by add excessive lithium and manganese in ternary system, form lithium-rich manganese-based solid solution, the form that can obtain having high power capacity is aLi2MnO3 (1-a) LiMO2 (0≤a≤0.7, M=Mn, Ni, Co) lithium-rich manganese-based anode material for lithium-ion batteries.Under the electrochemical window of 2.0～4.8V, it can emit capacity more than about 260mAh/g to this material, is considered to one of anode material for lithium ion battery with high power capacity of tool application prospect.But the poorly conductive of such lithium-rich manganese-based anode material for lithium-ion batteries own, makes the performance under high current charge-discharge still not ideal enough, does not reach the requirement of practical application.Particularly due to the existence of the lower Li2MnO3 phase of conductivity and the lattice degree of order producing in activation process first decline, the transmission of lithium ion is affected, thereby the high rate performance of such lithium-rich manganese-based anode material for lithium-ion batteries become one of bottleneck of its practical application.
The method of the lithium-rich manganese-based anode material for lithium-ion batteries of this class of conventional preparation mainly contains: coprecipitation, microwave heating method, sol-gal process, ion-exchange, solid reaction process etc.The pattern of controlling material by different preparation methods has become the method for the lithium-rich manganese-based anode material for lithium-ion batteries high rate performance of a kind of effective raising.
Summary of the invention
The invention provides a kind of lithium-rich manganese-based anode material for lithium-ion batteries and preparation method, utilize sucrose in heat treatment process can produce the characteristic of a large amount of gases, coordinate the feature of the strong oxidizability of nitrate itself, the speed of controlling γ-ray emission obtains the lithium-rich manganese-based precursor of lithium ionic cell positive material of ternary with mesh structural porous pattern.Keep mesh structural porous pattern by high-temperature calcination forming in lithium-rich manganese-based anode material for lithium-ion batteries layer structure again, made to have between particle good contact, thereby can effectively improve the high rate performance of material.
The object of the invention is to realize by the following technical solutions, 1) first metal lithium salts, nickel salt, manganese salt and cobalt salt are dissolved in deionized water, be mixed to form transparent solution, in transparent solution, add sucrose again, stir until transparent, then by solution heating, constantly the moisture content in solution is removed in stirring evaporation, first form colloidal sol, finally obtain gel; 2) this gel is calcined to 2h～4h for the first time at 500 DEG C～550 DEG C and remove organic principle, after grinding, calcine for the second time 15h～20h at 800 DEG C～900 DEG C again, obtain lithium-rich manganese-based anode material for lithium-ion batteries.
As preferably, the addition of described sucrose be in transparent solution total metal ion integral molar quantity 15%～25%.
Further, solution is heated to 70 DEG C～85 DEG C.
Tool of the present invention has the following advantages: lithium-rich manganese-based anode material for lithium-ion batteries of the present invention and preparation method, preparation process is simplified greatly compared with traditional coprecipitation, without the temperature, pH value, charging rate etc. of accurately controlling co-precipitation system.And the lithium-rich manganese-based anode material for lithium-ion batteries and the preparation method that obtain have mesh structural porous pattern, have effectively improved the contact between primary particle, have effectively improved the high rate performance of material.The lithium ion battery that utilizes the lithium-rich manganese-based anode material for lithium-ion batteries of the present invention and preparation method to make is applicable to the application such as electric automobile, hybrid vehicle, and can be provided permanent useful life.
Embodiment
Embodiment 1
Lithium-rich manganese-based anode material for lithium-ion batteries of the present invention, preparation process is made up of following steps: 1) first metal lithium salts, nickel salt, manganese salt and cobalt salt are dissolved in deionized water, be mixed to form transparent solution, in transparent solution, add sucrose again, stir until transparent, then by solution heating, constantly the moisture content in solution is removed in stirring evaporation, first form colloidal sol, finally obtain gel; 2) this gel is calcined to 2h～4h for the first time at 500 DEG C～550 DEG C and remove organic principle, after grinding, calcine for the second time 15h～20h at 800 DEG C～900 DEG C again, obtain lithium-rich manganese-based anode material for lithium-ion batteries.
The addition of described sucrose be in transparent solution total metal ion integral molar quantity 15%.
Solution is heated to 75 DEG C.
Embodiment 2
Lithium-rich manganese-based anode material for lithium-ion batteries of the present invention, preparation process is made up of following steps: 1) first metal lithium salts, nickel salt, manganese salt and cobalt salt are dissolved in deionized water, be mixed to form transparent solution, in transparent solution, add sucrose again, stir until transparent, then by solution heating, constantly the moisture content in solution is removed in stirring evaporation, first form colloidal sol, finally obtain gel; 2) this gel is calcined to 2h～4h for the first time at 500 DEG C～550 DEG C and remove organic principle, after grinding, calcine for the second time 15h～20h at 800 DEG C～900 DEG C again, obtain lithium-rich manganese-based anode material for lithium-ion batteries.
The addition of described sucrose be in transparent solution total metal ion integral molar quantity 25%.
Solution is heated to 85 DEG C.
Lithium-rich manganese-based anode material for lithium-ion batteries of the present invention and preparation method, preparation process is simplified greatly compared with traditional coprecipitation, without the temperature, pH value, charging rate etc. of accurately controlling co-precipitation system.And the lithium-rich manganese-based anode material for lithium-ion batteries and the preparation method that obtain have mesh structural porous pattern, have effectively improved the contact between primary particle, have effectively improved the high rate performance of material.The lithium ion battery that utilizes the lithium-rich manganese-based anode material for lithium-ion batteries of the present invention and preparation method to make is applicable to the application such as electric automobile, hybrid vehicle, and can be provided permanent useful life.
Claims (3)
1. lithium-rich manganese-based anode material for lithium-ion batteries and a preparation method, is characterized in that: comprise the following steps:
1) first metal lithium salts, nickel salt, manganese salt and cobalt salt are dissolved in deionized water, are mixed to form transparent solution, then add sucrose in transparent solution, stir until transparent, then by solution heating, constantly the moisture content in solution is removed in stirring evaporation, first form colloidal sol, finally obtain gel; 2) this gel is calcined to 2h～4h for the first time at 500 DEG C～550 DEG C and remove organic principle, after grinding, calcine for the second time 15h～20 h at 800 DEG C～900 DEG C again, obtain lithium-rich manganese-based anode material for lithium-ion batteries.
2. lithium-rich manganese-based anode material for lithium-ion batteries according to claim 1 and preparation method, is characterized in that step 1) in, the addition of described sucrose be in transparent solution total metal ion integral molar quantity 15%～25%.
3. lithium-rich manganese-based anode material for lithium-ion batteries according to claim 1 and preparation method, is characterized in that step 1) in, solution is heated to 70 DEG C～85 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105489842A (en) * | 2015-12-18 | 2016-04-13 | 浙江天能能源科技有限公司 | Lithium-rich manganese-based cathode material and preparation method thereof |
| CN110165169A (en) * | 2019-05-16 | 2019-08-23 | 复旦大学 | A kind of preparation method of porous flake nickel-cobalt-manganternary ternary anode material |
-
2014
- 2014-08-06 CN CN201410384411.5A patent/CN104201334A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105489842A (en) * | 2015-12-18 | 2016-04-13 | 浙江天能能源科技有限公司 | Lithium-rich manganese-based cathode material and preparation method thereof |
| CN105489842B (en) * | 2015-12-18 | 2018-03-23 | 浙江天能能源科技股份有限公司 | A kind of lithium-rich manganese-based anode material and preparation method thereof |
| CN110165169A (en) * | 2019-05-16 | 2019-08-23 | 复旦大学 | A kind of preparation method of porous flake nickel-cobalt-manganternary ternary anode material |
| CN110165169B (en) * | 2019-05-16 | 2022-09-16 | 复旦大学 | Preparation method of porous flaky nickel-cobalt-manganese ternary cathode material |
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Application publication date: 20141210 |