CN105304880A - Mixed cathode material for lithium-ion battery - Google Patents
Mixed cathode material for lithium-ion battery Download PDFInfo
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- CN105304880A CN105304880A CN201510839939.1A CN201510839939A CN105304880A CN 105304880 A CN105304880 A CN 105304880A CN 201510839939 A CN201510839939 A CN 201510839939A CN 105304880 A CN105304880 A CN 105304880A
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/364—Composites as mixtures
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
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- 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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- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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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 mixed cathode material for a lithium ion battery and a preparation method of the mixed cathode material. The mixed cathode material comprises an NCA cathode material and an LFPO cathode material, wherein the stoichiometric ratio of the NCA cathode material to the LFPO cathode material is (9-7):(1:3); the NCA cathode material is LiNi0.8Co0.15Al0.05O2, grains of the NCA cathode material are spherical, and the average grain diameter is preferably 14 [mu]m; the LFPO cathode material is LiFePO4, and the average grain diameter of grains of the LFPO cathode material is preferably 80 nm. The invention also provides the preparation method of the mixed cathode material for the lithium ion battery. The mixed cathode material for the lithium ion battery and the preparation method of the mixed cathode material are simple in process and easy for industrial production, and the safety performance and the cycle performance, particularly the cycle performance at high temperature, of the cathode material are improved.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof, particularly, relate to a kind of lithium ion battery blended anode material and preparation method thereof.
Background technology
Compared with traditional zinc-silver oxide cell, ickel-cadmium cell, Ni-H cell, the outstanding advantages such as lithium ion battery has that specific energy is high, operating voltage is high, temperature limit is wide, self discharge efficiency is low, has extended cycle life, memory-less effect, be widely used in mobile phone, notebook computer and other portable electronics, and progressively to high-power system as the field such as electric automobile, intelligent grid, satellite and distributed energy resource system is expanded.From current development situation, countries in the world also all propose Long-and Medium-term Development planning to high-energy-density chemical energy storage power supply, such as the specific energy target of recent lithium ion battery is defined as 250 ~ 300Wh/kg by NASA and SAFT etc., also represents to the energy density of the year two thousand twenty energy type lithium ion battery and will reach 250Wh/kg in Japanese NEDO power battery of electric vehicle development plan.But the energy density of lithium ion battery is mainly limited to positive electrode, because the carbon material used as anode specific capacity of commercialization is at about 300 ~ 350mAh/g, and common positive electrode (comprises LiCoO
2, LiNiO
2, spinel-type LiMn
2o
4, stratiform LiMnO
2, LiFePO
4, Li [Ni
1/3co
1/3mn
1/3] O
2deng) specific capacity be 120 ~ 165mAh/g, far below the theoretical capacity of negative material.In recent years, NCA(nickel cobalt lithium aluminate) material is because of its high power capacity, low cost, of low pollution and receive the concern of people.Sony adopts NCA material to be assembled into battery and tests, and after the charge and discharge circulation 270 times of 0.5C, capacity is the capability retention that the battery of 10Ah still has 90%.In flexible-packed battery, the energy density of this material is own through reaching 150Wh/kg, and application prospect is very optimistic.
Although NCA positive electrode has considerable specific energy, reach the requirement of practical application, but still there are some urgent problems in it: the electrical efficiency of cycle charge discharge first that (1) is caused by cation mixing is low and structural stability is poor; (2) charging produces the Ni of strong oxidizing property latter stage
4+with electrolyte generation side reaction, divide and parse accessory substance O
2, bring potential safety hazard; (3) basicity of nickel system positive electrode own is large, and rough surface, cause its very easily moisture absorption, storge quality is poor.Be directed to the poor cycle performance of NCA material and security performance; current topmost method of modifying carries out coated to it; barrier material itself contacts with the direct of air with electrolyte; thus improve the cycle performance of material; but this method of modifying technique relative complex, is unfavorable for that industrial scale is produced.
Summary of the invention
The object of this invention is to provide a kind of for lithium ion battery blended anode material, improve security performance and the cycle performance of NCA material, cycle performance especially at high temperature.
In order to achieve the above object, the invention provides a kind of lithium ion battery blended anode material, wherein, this positive electrode comprises NCA positive electrode and LFPO positive electrode; Described NCA positive electrode and the stoichiometric proportion of LFPO positive electrode are 9:1 ~ 7:3.
Above-mentioned lithium ion battery blended anode material, wherein, described NCA positive electrode is LiNi
0.8co
0.15al
0.05o
2.
Above-mentioned lithium ion battery blended anode material, wherein, described NCA positive electrode, its crystal grain is spherical.
Above-mentioned lithium ion battery blended anode material, wherein, described NCA positive electrode, average grain diameter is 12 ~ 16 μm.
Above-mentioned lithium ion battery blended anode material, wherein, described NCA positive electrode, average grain diameter is 14 μm.
Above-mentioned lithium ion battery blended anode material, wherein, described LFPO positive electrode is LiFePO
4.
Above-mentioned lithium ion battery blended anode material, wherein, described LFPO positive electrode, the average grain diameter of particle is 60 ~ 100nm.
Above-mentioned lithium ion battery blended anode material, wherein, described LFPO positive electrode, the average grain diameter of particle is 80nm.
Present invention also offers a kind of preparation method of above-mentioned lithium ion battery blended anode material, wherein, described method comprises: step 1, in proportion precise NCA positive electrode and LFPO positive electrode; Described NCA positive electrode and the stoichiometric proportion of LFPO positive electrode are 9:1 ~ 7:3; Step 2, carries out ball milling by load weighted material mixing, obtains composite material, as the positive active material of lithium ion battery.
The preparation method of above-mentioned lithium ion battery blended anode material, wherein, the ball milling described in step 2, be that load weighted material is put into ball grinder ball milling 1 ~ 2 hour, rotational speed of ball-mill is 100rpm.
Lithium ion battery blended anode material provided by the invention and preparation method thereof has the following advantages:
Adopt NCA(nickel cobalt lithium aluminate first) and LFPO(LiFePO4) two kinds of materials mix as positive electrode active materials, the security performance utilizing LiFePO 4 material good and cycle performance make up the shortcoming of NCA positive electrode poor stability, keep the high specific discharge capacity of NCA material simultaneously, using the two mixing as anode material for lithium ion battery, make it the demand being more suitable for market.This blended anode material preparation method is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of raw material selected by the embodiment of the present invention 1 and prepared lithium ion battery blended anode material.
Fig. 2 is the X-ray diffractogram of the lithium ion battery blended anode material prepared by the embodiment of the present invention 1.
Fig. 3 be lithium ion battery blended anode material initial charge prepared by the embodiment of the present invention 1 completely after differential thermal analysis curve.
Fig. 4 is the cyclic voltammetry curve of the lithium ion battery blended anode material prepared by the embodiment of the present invention 1.
Fig. 5 is the cycle performance curve chart under the lithium ion battery blended anode material high temperature prepared by the embodiment of the present invention 1.
Fig. 6 be lithium ion battery blended anode material initial charge prepared by the embodiment of the present invention 1 completely after impedance diagram.
Fig. 7 is the first charge-discharge curve of the lithium ion battery blended anode material prepared by the embodiment of the present invention 3.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is further described.
Lithium ion battery blended anode material provided by the invention, comprises NCA positive electrode and LFPO positive electrode.
The stoichiometric proportion of NCA positive electrode and LFPO positive electrode is 9:1 ~ 7:3.
NCA positive electrode is LiNi
0.8co
0.15al
0.05o
2, its crystal grain is spherical, and average grain diameter is 12 ~ 16 μm, is preferably 14 μm.
LFPO positive electrode is LiFePO
4, the average grain diameter of particle is 60 ~ 100nm, is preferably 80nm.
Present invention also offers the preparation method of this lithium ion battery blended anode material, comprise: step 1, in proportion precise NCA positive electrode and LFPO positive electrode; The stoichiometric proportion of NCA positive electrode and LFPO positive electrode is 9:1 ~ 7:3; Step 2, ball grinder is put in load weighted material mixing and carries out ball milling 1 ~ 2 hour, rotational speed of ball-mill is 100rpm.The composite material obtained, as the positive active material of lithium ion battery.
By the following examples embodiments of the present invention are described in detail.
Embodiment 1
Step 1, according to stoichiometric proportion 9:1 precise NCA and LFPO positive electrode, step 2, puts into ball grinder ball milling one hour by load weighted material, obtain composite material sample, as active substance of lithium ion battery anode.
NCA, LFPO positive electrode and the SEM(ESEM of blended anode material obtained by the present embodiment) figure as shown in Figure 1, A is NCA positive electrode, and B is LFPO positive electrode, and C is blended anode material.As can be seen from the figure the pattern of NCA positive electrode itself is not damaged substantially, is attached to NCA anode material spherical particle surface to LFPO positive electrode uniform particles.
The XRD(X x ray diffraction of the blended anode material obtained by the present embodiment) figure as shown in Figure 2, A is NCA positive electrode, and B is blended anode material.As can be seen from the figure blended anode material comprises the diffraction maximum of NCA and LFPO two kinds of positive electrodes, does not in addition occur other assorted peaks.
As shown in Figure 3, A is NCA positive electrode to differential thermal analysis (DSC) curve after the blended anode material initial charge obtained by the present embodiment is complete, and B is blended anode material.As can be seen from the figure the heat decomposition temperature of blended anode material is higher than NCA positive electrode, improves the thermal stability of material.
As shown in Figure 4, A is first circle to cyclic voltammetric (CV) curve chart of the blended anode material obtained by the present embodiment, and B is the 3rd circle.The redox peak of NCA positive electrode and the redox peak (3.4V) of LFPO positive electrode clearly can be told from figure.
The cycle performance curve of the blended anode material obtained by the present embodiment at 50 DEG C as shown in Figure 5,50 DEG C, carries out discharge and recharge with the electric current of 0.5C, and voltage range 2.8-4.3V, A are NCA positive electrode, and B is blended anode material.As can be seen from the figure, the discharge capacity first of traditional NCA positive electrode is 182.8mAh/g, and after circulating 200 weeks, capability retention is 89.5%; The discharge capacity first of blended anode material is 205.6mAh/g, and after circulating 200 weeks, capability retention reaches 98.1%, and the cycle performance under high temperature has significant lifting.
Embodiment 2
Step 1, according to stoichiometric proportion 8:2 precise NCA and LFPO positive electrode, step 2, puts into ball grinder ball milling one hour by load weighted material, obtain composite material sample, as active substance of lithium ion battery anode.
As shown in Figure 6, A is NCA positive electrode to impedance (EIS) curve chart after the blended anode material initial charge obtained by the present embodiment is complete, and B is blended anode material.Can find out that interface impedance and the Charge-transfer resistance of blended anode material are obtained for reduction, more be conducive to the transmission of charge and discharge process intermediate ion.
Embodiment 3
Step 1, according to stoichiometric proportion 7:3 precise NCA and LFPO positive electrode, step 2, puts into ball grinder ball milling one hour by load weighted material, obtain composite material sample, as active substance of lithium ion battery anode.
The composite material sample first charge-discharge curve obtained by the present embodiment as shown in Figure 7, carries out discharge and recharge with the electric current of 0.1C, can find out that the initial coulomb efficiency of composite material is 87.6%, higher than 83.7% of simple NCA material.Illustrate that blended anode material has higher initial coulomb efficiency.
Lithium ion battery blended anode material provided by the invention and preparation method thereof, adopt NCA and LFPO two kinds of material mixing as positive electrode active materials first, LFPO positive electrode grain diameter reaches nanoscale, and NCA anode material spherical second particle average grain diameter is at about 14 μm, utilize this feature, by physical mixed, short grained LFPO homogenize material can be attached to NCA positive electrode.Also the good security performance of LiFePO 4 material and cycle performance can be made full use of like this while the high specific discharge capacity keeping NCA material, the battery of preparation with single use NCA or LiFePO4 as positive electrode battery compared with, possess high discharge capacity, good cycle performance (cycle performance particularly under high temperature), excellent security performance thus make up the shortcoming of NCA positive electrode poor stability, make it the demand being more suitable for market.This blended anode material preparation method is simple, is easy to suitability for industrialized production.
Although content of the present invention has done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple amendment of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. a lithium ion battery blended anode material, is characterized in that, this positive electrode comprises NCA positive electrode and LFPO positive electrode; Described NCA positive electrode and the stoichiometric proportion of LFPO positive electrode are 9:1 ~ 7:3.
2. lithium ion battery blended anode material as claimed in claim 1, it is characterized in that, described NCA positive electrode is LiNi
0.8co
0.15al
0.05o
2.
3. lithium ion battery blended anode material as claimed in claim 2, it is characterized in that, described NCA positive electrode, its crystal grain is spherical.
4. lithium ion battery blended anode material as claimed in claim 3, it is characterized in that, described NCA positive electrode, average grain diameter is 12 ~ 16 μm.
5. lithium ion battery blended anode material as claimed in claim 4, it is characterized in that, described NCA positive electrode, average grain diameter is 14 μm.
6. lithium ion battery blended anode material as claimed in claim 1, it is characterized in that, described LFPO positive electrode is LiFePO
4.
7. lithium ion battery blended anode material as claimed in claim 6, it is characterized in that, described LFPO positive electrode, the average grain diameter of particle is 60 ~ 100nm.
8. lithium ion battery blended anode material as claimed in claim 7, it is characterized in that, described LFPO positive electrode, the average grain diameter of particle is 80nm.
9. as a preparation method for the lithium ion battery blended anode material in claim 1 ~ 8 as described in any one, it is characterized in that, described method comprises:
Step 1, in proportion precise NCA positive electrode and LFPO positive electrode; Described NCA positive electrode and the stoichiometric proportion of LFPO positive electrode are 9:1 ~ 7:3;
Step 2, carries out ball milling by load weighted material mixing, obtains composite material, as the positive active material of lithium ion battery.
10. the preparation method of lithium ion battery blended anode material as claimed in claim 9, it is characterized in that, the ball milling described in step 2, be that load weighted material is put into ball grinder ball milling 1 ~ 2 hour, rotational speed of ball-mill is 100rpm.
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|---|---|---|---|
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ID=55201858
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|---|---|---|---|---|
| CN109417162A (en) * | 2018-09-28 | 2019-03-01 | 宁波致良新能源有限公司 | Anode additive and preparation method thereof, anode and preparation method thereof and lithium ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104577093A (en) * | 2015-01-13 | 2015-04-29 | 海宁美达瑞新材料科技有限公司 | Surface coating modified lithium ion battery cathode material and preparation method thereof |
| CN104600242A (en) * | 2014-12-26 | 2015-05-06 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery composite positive material, positive plate and lithium ion battery |
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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600242A (en) * | 2014-12-26 | 2015-05-06 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery composite positive material, positive plate and lithium ion battery |
| CN104577093A (en) * | 2015-01-13 | 2015-04-29 | 海宁美达瑞新材料科技有限公司 | Surface coating modified lithium ion battery cathode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HYUN-JU KIM ET AL.: ""Electrochemical Properties and Thermal Stability of LiNi0.8Co0.15Al0.05O2-LiFePO4 Mixed Cathode Materials for Lithium Secondary Batteries"", 《JOURNAL OF ELECTROCHEMICAL SCIENCE AND TECHNOLOGY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109417162A (en) * | 2018-09-28 | 2019-03-01 | 宁波致良新能源有限公司 | Anode additive and preparation method thereof, anode and preparation method thereof and lithium ion battery |
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