CN108574090A - A kind of lithium ion battery negative material and preparation method thereof - Google Patents
A kind of lithium ion battery negative material and preparation method thereof Download PDFInfo
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- CN108574090A CN108574090A CN201810204721.2A CN201810204721A CN108574090A CN 108574090 A CN108574090 A CN 108574090A CN 201810204721 A CN201810204721 A CN 201810204721A CN 108574090 A CN108574090 A CN 108574090A
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- transition metal
- lithium ion
- ion battery
- battery negative
- negative material
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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 kind of lithium ion battery negative materials, including transition metal oxide and the transition metal in transition metal oxide.The invention discloses above-mentioned lithium ion battery negative material preparation methods, include the following steps：Dissolving in solvent is added in transition metal salt and obtains material a；Dispersion in solvent is added in precipitating reagent and obtains material b；Hybrid reaction in material b is added in material a and obtains transition metal salt presoma；Transition metal salt presoma is calcined under calcination atmosphere and obtains lithium ion battery negative material.Gained negative material of the invention has the 3-D nano, structure of higher specific surface and larger volume ratio, the integrality in the space and holding structure needed for volume expansion can be provided during lithiumation, improve conduction efficiency of the electronics in transition metal oxide, the electric conductivity for improving combination electrode material, to improve the high rate performance and cycle performance of material.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of lithium ion battery negative material and its preparation sides
Method.
Background technology
With the fast development of mobile electronic device and electric vehicle, lithium ion battery is since it is high with specific capacity, follows
Ring long lifespan, it is environmental-friendly, cheap the advantages that be concerned.Carbon negative electrode material of lithium ion cell is relatively low because of theoretical specific capacity
(372mAh/g), and cycle performance and high rate performance are poor, have been unable to meet current social development to next-generation lithium ion battery
The demand of energy density.Therefore, there is an urgent need for developing, specific capacity is high, high rate performance is excellent, good cycle negative electrode of lithium ion battery
Material.Transition metal oxide due to its higher theoretical specific capacity, excellent security performance and it is cheap the advantages that
Through causing extensive interest.
Invention content
Technical problems based on background technology, the present invention propose a kind of lithium ion battery negative material and its preparation
Method, gained negative material have the 3-D nano, structure of higher specific surface and larger volume ratio, can be in lithiumation process
The integrality in space and holding structure needed for middle offer volume expansion improves conduction of the electronics in transition metal oxide
Efficiency improves the electric conductivity of combination electrode material, to improve the high rate performance and cycle performance of material.
A kind of lithium ion battery negative material proposed by the present invention, including transition metal oxide be embedded in oxo transition metal
Transition metal in compound.
Above-mentioned lithium ion battery negative material preparation method proposed by the present invention, includes the following steps：
S1, dissolving in transition metal salt addition solvent is obtained into material a；
S2, precipitating reagent is added in solvent and disperses to obtain material b；
S3, hybrid reaction in material a addition materials b is obtained into transition metal salt presoma；
S4, it transition metal salt presoma is calcined under calcination atmosphere obtains lithium ion battery negative material.
Preferably, in S1, the anion of transition metal salt is acetate ion and/or sulfate ion.
Preferably, in S2, precipitating reagent is oxalic acid or sodium bicarbonate.
Preferably, in S2, jitter time 10-30min.
Preferably, in S3, the hybrid reaction time is 2.5-3.5h.
Preferably, in S4, calcination atmosphere is argon gas-hydrogen mixed gas atmosphere.
Preferably, in S4, calcination temperature is 480-520 DEG C, calcination time 2.5-3.5h.
Gained lithium ion battery negative material of the invention, the nanometer being embedded by transition metal in transition metal oxide
The multistage micrometer structure that grain is formed, the 3-D nano, structure with higher specific surface and larger volume ratio, can be in lithium
The integrality in the space and holding structure needed for volume expansion is provided during changing；And transition metal is embedded into oxo transition metal
The structure of compound nano particle can be limited in cyclic process particle movement, reunite and can be more in redox reaction
The volume expansion and contraction that good adaptation generates；Importantly, the metal of embedded high conductivity can improve electronics in transition
Conduction efficiency in metal oxide improves the electric conductivity of combination electrode material, to improve the high rate performance and cycle of material
Performance.
Description of the drawings
Fig. 1 is the battery high rate performance of 1 gained lithium ion battery negative material of the embodiment of the present invention.
Fig. 2 is the battery high rate performance of 1 gained MnO negative materials of comparative example.
Fig. 3 is the cycle performance of battery of 1 gained lithium ion battery negative material of the embodiment of the present invention.
Fig. 4 is the cycle performance of battery of 1 gained MnO negative materials of comparative example.
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of lithium ion battery negative material preparation method, includes the following steps：
S1, it manganese sulfate is added to the water to dissolving obtains material a；
S2, by oxalic acid be added to the water dispersion 10min obtain material b；
S3, hybrid reaction 3.5h in material b is added in material a, obtains transition metal salt presoma；
S4, by transition metal salt presoma under argon gas-hydrogen mixed gas atmosphere, 480 DEG C calcining 3.5h, obtain lithium-ion electric
Pond negative material.
Embodiment 2
A kind of lithium ion battery negative material preparation method, includes the following steps：
S1, dissolving in nickel sulfate addition ethyl alcohol is obtained into material a；
S2, dispersion 30min in oxalic acid addition ethyl alcohol is obtained into material b；
S3, hybrid reaction 2.5h in material b is added in material a, obtains transition metal salt presoma；
S4, by transition metal salt presoma under argon gas-hydrogen mixed gas atmosphere, 520 DEG C calcining 2.5h, obtain lithium-ion electric
Pond negative material.
Embodiment 3
A kind of lithium ion battery negative material preparation method, includes the following steps：
S1, it is 1 in molar ratio by nickel acetate and manganese acetate：Dissolving obtains material a in 10 addition 100mL deionized waters；
S2, dispersion 30min in sodium bicarbonate addition 100mL deionized waters is obtained into material b；
S3, hybrid reaction 3h in material b is added in material a, by gained sediment deionized water and ethyl alcohol centrifuge washing,
100 DEG C of drying obtain yellow powder MCO3·xH2O (M=Ni, Mn) presoma；
S4, by MCO3·xH2Under argon gas-hydrogen mixed gas atmosphere, 500 DEG C of calcining 3h are obtained O (M=Ni, Mn) presomas
Lithium ion battery negative material；Wherein in argon gas-hydrogen mixed gas atmosphere, the volume ratio of argon gas and hydrogen is 95：5.
It carries out lithium ion battery negative material obtained by the present embodiment to detain electric making, then carries out high rate performance test,
The results are shown in Figure 1, carries out high temperature cyclic performance test, the results are shown in Figure 3.By Fig. 1 and Fig. 3 it is found that 5C times of battery is put
Specific capacity is 214.3mAh/g；It is 72% that 0.5C, which recycles 200 weeks capacity retention ratios,.
Comparative example 1
Manganese acetate is dissolved in 100mL deionized waters, 0.5h is stirred, obtains acetate solution；Sodium bicarbonate is dissolved
In 100mL deionized waters, 0.5h is stirred, NaHCO is obtained3Solution；Above-mentioned NaHCO is added in above-mentioned acetate solution3Solution
In, reaction 3h obtains Huang by gained sediment deionized water and ethyl alcohol centrifuge washing, and in 100 DEG C of drying after reaction
The powdered MnCO of color3·xH2O presomas；By above-mentioned MnCO3·xH2O presomas calcine 3h for 500 DEG C under an argon atmosphere, obtain
MnO negative materials.
MnO negative materials are carried out to detain electric making, then carry out high rate performance test, the results are shown in Figure 2, carries out high
Warm cycle performance test, the results are shown in Figure 4.By Fig. 2 and Fig. 4 it is found that it is 40.81mAh/g that 5C times of battery, which puts specific capacity,；
It is 45% that 0.5C, which recycles 200 weeks capacity retention ratios,.
It is compared from embodiment 3 and comparative example 1：When low-rate discharge, times of the insertion of transition metal to negative material
The influence very little of performance is put, but when discharge-rate is higher, higher to negative material conduction needs, transition metal has higher
Conductivity, thus more advantage；The structure that transition metal is embedded into transition metal oxide nano particle can be in cyclic process
The movement of middle limitation particle and reunion and preferably adapt to the volume expansion and contraction generated in redox reaction.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of lithium ion battery negative material, which is characterized in that including transition metal oxide and be embedded in transiting metal oxidation
Transition metal in object.
2. a kind of lithium ion battery negative material preparation method as described in claim 1, which is characterized in that include the following steps：
S1, dissolving in transition metal salt addition solvent is obtained into material a；
S2, precipitating reagent is added in solvent and disperses to obtain material b；
S3, hybrid reaction in material a addition materials b is obtained into transition metal salt presoma；
S4, it transition metal salt presoma is calcined under calcination atmosphere obtains lithium ion battery negative material.
3. lithium ion battery negative material preparation method according to claim 2, which is characterized in that in S1, transition metal salt
Anion be acetate ion and/or sulfate ion.
4. according to lithium ion battery negative material preparation method described in Claims 2 or 3, which is characterized in that in S2, precipitating reagent is
Oxalic acid or sodium bicarbonate.
5. according to any one of the claim 2-4 lithium ion battery negative material preparation methods, which is characterized in that in S2, point
It is 10-30min to dissipate the time.
6. according to any one of the claim 2-5 lithium ion battery negative material preparation methods, which is characterized in that in S3, mix
The conjunction reaction time is 2.5-3.5h.
7. according to any one of the claim 2-6 lithium ion battery negative material preparation methods, which is characterized in that in S4, forge
Burning atmosphere is argon gas-hydrogen mixed gas atmosphere.
8. according to any one of the claim 2-7 lithium ion battery negative material preparation methods, which is characterized in that in S4, forge
It is 480-520 DEG C to burn temperature, calcination time 2.5-3.5h.
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| CN201810204721.2A CN108574090A (en) | 2018-03-13 | 2018-03-13 | A kind of lithium ion battery negative material and preparation method thereof |
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| CN201810204721.2A CN108574090A (en) | 2018-03-13 | 2018-03-13 | A kind of lithium ion battery negative material and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104037389A (en) * | 2014-06-19 | 2014-09-10 | 合肥国轩高科动力能源股份公司 | Transition-metal-oxide negative electrode material of lithium ion battery and preparation method of material |
| CN106252651A (en) * | 2016-11-01 | 2016-12-21 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of lithium ion battery porous composite negative pole material and preparation method thereof |
| CN107293705A (en) * | 2017-05-10 | 2017-10-24 | 华南农业大学 | Lithium ion battery bamboo charcoal/metal oxide composite cathode material and its preparation method and application |
-
2018
- 2018-03-13 CN CN201810204721.2A patent/CN108574090A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104037389A (en) * | 2014-06-19 | 2014-09-10 | 合肥国轩高科动力能源股份公司 | Transition-metal-oxide negative electrode material of lithium ion battery and preparation method of material |
| CN106252651A (en) * | 2016-11-01 | 2016-12-21 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of lithium ion battery porous composite negative pole material and preparation method thereof |
| CN107293705A (en) * | 2017-05-10 | 2017-10-24 | 华南农业大学 | Lithium ion battery bamboo charcoal/metal oxide composite cathode material and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 孙永辉等: ""控制还原法制备高性能MnO@Ni 锂离子电池负极材料"", 《硅酸盐学报》 * |
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Application publication date: 20180925 |