CN104733719A - Method for preparing germanium-based cathode material for lithium ion battery by adopting carbothermic reduction method - Google Patents
Method for preparing germanium-based cathode material for lithium ion battery by adopting carbothermic reduction method Download PDFInfo
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- CN104733719A CN104733719A CN201310731643.9A CN201310731643A CN104733719A CN 104733719 A CN104733719 A CN 104733719A CN 201310731643 A CN201310731643 A CN 201310731643A CN 104733719 A CN104733719 A CN 104733719A
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- germanium
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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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- 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 relates to a method for preparing a germanium-based cathode material for a lithium ion battery by adopting a carbothermic reduction method. The method is characterized by comprising the following steps: 1, ball milling the mixture of germanium dioxide, graphite and coal asphalt in a weight ratio of 10: 7: 12 in an ethanol solution, and heating and extracting the ethanol solution to obtain a precursor of asphalt and graphite mixed carbon-cladding germanium dioxide; and placing the precursor prepared in the step 1 in a high-temperature furnace, heating the precursor at speed of 5 DEG C per minute in an argon atmosphere to 800 to 900 DEG C, sintering the precursor for 5h, and then naturally cooling the precursor. According to the method, the germanium oxide and carbon material are used as raw materials to be ball milled and sintered at 800 to 900 DEG C, and thorough carbothermic reduction is carried out on an electrochemical active substance GeO2 to form the germanium-graphite-carbon germanium-based cathode material. The method is simple in production step and low in production cost; the prepared material is good in coating effect, high in charging-discharging capacity retention rate and suitable for the commercialized mass production.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, particularly relate to a kind of method that lithium ion battery germanium base negative material is prepared in carbon thermal reduction.
Background technology
From the nineties in last century, Sony company uses Sheet Graphite to replace the metal Li of fail safe extreme difference, since being successfully prepared the first lithium rechargeable battery that can fill, lithium ion battery is because of its high-energy-density, pollution-free, range of application obtains develop rapidly, expands the field such as electric tool, electric automobile to from mobile communication power supply, notebook computer, video camera etc.And the electrochemistry capacitance of existing Carbon anode is on the low side, the further requirement to portable secondary battery performance of development in science and technology can not be met.
As the 4th major element, Si, Sn, Ge, Pb etc. have certain Electrochemical lithiation ability.Si and Sn material has carried out large quantifier elimination, and Sn-Co-C composite material has been carried out Commercialization application by Japanese Sony company; But lower (the 999mAh g of the embedding lithium of the theory due to Sn capacity
-1), after Combined Processing, relative to material with carbon element, the room for improvement on capacity is less; Silicon materials due to its electrochemical reversible capacity high, fail safe is good, the advantages such as aboundresources, but the change in volume of silicon materials in Electrochemical lithiation process is excessive, and first charge-discharge efficiency is lower, the serious practical application hindering this electrode material.
And the embedding lithium capacity of the theory of Ge material is 1600mAh g
-1, the change in volume in removal lithium embedded process is less than Si material, should substitute material with carbon element, becomes new lithium ion battery negative material.But because its reserves are less, expensive, receive publicity less.At present, solar cell uses Ge in a large number, must have a large amount of corner blanking containing a large amount of Ge and defective item occurs, and lithium ion battery will be far smaller than solar cell for the purity of material, have a lot of resource to utilize, this reduces cost to a certain extent.
Current known lithium ion battery Ge base negative material preparation process is loaded down with trivial details, and considerable part is thin-film material, and produce and amplify difficulty, cost is high, and the material capacity conservation rate of preparation is poor, has decay in various degree.
Summary of the invention
The present invention provides that a kind of charge/discharge capacity conservation rate is high, good cycling stability for solving in known technology the technical problem that exists, the energy density of the lithium ion battery made is high, and the making step of material is simple, cost is low, and the method for lithium ion battery germanium base negative material is prepared in the carbon thermal reduction being applicable to large-scale commercial production.
The present invention includes following technical scheme:
The method of lithium ion battery germanium base negative material is prepared in carbon thermal reduction, is characterized in: comprise following preparation process:
Step 1: by weight ratio germanium dioxide: graphite: coal tar pitch=10:7:12, ball milling in ethanolic solution, heating detaches ethanolic solution, obtains the presoma of pitch, the coated germanium dioxide of graphite mixing charcoal;
Step 2: presoma step 1 made is placed in high temperature furnace, is warming up to 800-900 DEG C with the programming rate of 5 DEG C/min under argon gas atmosphere, sintering 5h, after Temperature fall cooling, namely forms carbon thermal reduction of the present invention and prepares lithium ion battery germanium base negative material.
The present invention can also adopt following technical measures:
The weight of described germanium dioxide, graphite, coal tar pitch and be 29g:100ml with the volume ratio of ethanol.
Described Ball-milling Time is 60 hours.
The advantage that the present invention has and good effect:
The present invention has selected germanium oxide, material with carbon element as raw material, by the sintering of ball milling and 800-900 DEG C, to electroactive substance GeO
2carry out carbon heat reducing thoroughly, generate the chemical property of electroactive substance elemental Germanium, the reaction that material occurs is lithium alloyage reaction, define the germanium base negative material of germanium-graphite-carbon, not only making step be simple in the present invention, the cost of manufacture that reduces material, and the Material coating made is effective, charge/discharge capacity conservation rate is high, good cycling stability, effectively can improve the energy density of lithium ion battery, is applicable to large-scale commercial and produces.
Accompanying drawing explanation
Fig. 1 is electrode material electrochemistry cyclic process curve chart prepared by the embodiment of the present invention 1;
Fig. 2 is the first all charge discharge conditional curve figure of electrode material prepared by the embodiment of the present invention 1.
Fig. 3 is the embodiment of the present invention 1, electrode material XRD collection of illustrative plates prepared by embodiment 2.
Embodiment
For summary of the invention of the present invention, Characteristic can be disclosed further, be described in detail as follows especially exemplified by following instance.
The method of lithium ion battery germanium base negative material is prepared in carbon thermal reduction, is characterized in: comprise following preparation process:
Step 1: by weight ratio germanium dioxide: graphite: coal tar pitch=10:7:12, ball milling in ethanolic solution, heating detaches ethanolic solution, obtains the presoma of pitch, the coated germanium dioxide of graphite mixing charcoal;
Step 2: presoma step 1 made is placed in high temperature furnace, is warming up to 800-900 DEG C with the programming rate of 5 DEG C/min under argon gas atmosphere, sintering 5h, after Temperature fall cooling, namely forms carbon thermal reduction of the present invention and prepares lithium ion battery germanium base negative material.
The weight of described germanium dioxide, graphite, coal tar pitch and be 29g:100ml with the volume ratio of ethanol.
Described Ball-milling Time is 60 hours.
Embodiment 1:
Step 1: by 10g germanium dioxide (GeO
2), 7g graphite, 12g coal tar pitch, ball milling 60 hours in 100ml ethanolic solution, heating detach ethanolic solution, obtain the presoma of pitch, the coated germanium dioxide of graphite mixing charcoal;
Step 2: presoma step 1 made is placed in high temperature furnace, the lower 5 DEG C/min of argon gas atmosphere is warmed up to 900 DEG C, high temperature sintering 5h, after Temperature fall cooling, namely forms carbon thermal reduction of the present invention and prepares lithium ion battery germanium base negative material.
Cyclic test in 50 weeks test is carried out to the material that embodiment 1 is made, as in Fig. 1 electrochemistry cyclic process curve chart, first all charge discharge conditional curve figure find out with Fig. 2, lithium ion battery germanium base negative material prepared by the present invention, specific discharge capacity is greater than 500mAh/g, is more than 1.5 times of conventional carbon material; Present invention achieves the features such as material making step is simple, capacity high good cycling stability; In Fig. 3, lower curve is electrode material XRD collection of illustrative plates prepared by embodiment 1, in Fig. 3, upper curve is electrode material XRD collection of illustrative plates prepared by embodiment 2, as seen in Figure 3, except faint material with carbon element diffraction maximum, be entirely the diffractive features peak of germanium, illustrate that, under suitable heating-up temperature, germanium oxide can be reduced completely by carbon.
Embodiment 2:
Step 1: by 10g germanium dioxide, 7g graphite, 12g coal tar pitch, ball milling 60 hours in 100ml ethanolic solution, heating detaches ethanolic solution, obtains the presoma of pitch, the coated germanium dioxide of graphite mixing charcoal;
Step 2: presoma step 1 made is placed in high temperature furnace, the lower 5 DEG C/min of argon gas atmosphere is warmed up to 800 DEG C, high temperature sintering 5h, after Temperature fall cooling, namely forms carbon thermal reduction of the present invention and prepares lithium ion battery germanium base negative material.
Carry out cyclic test in 50 weeks test to the material that embodiment 2 is made, specific discharge capacity remains at more than 550mAh/g.
Comparative example 1:
Step 1: select that mean roughness is 0.5 micron, thickness be the coarse Copper Foil of 18 microns as the material of deposit Germanium molybdenum alloy, remove the oxide of copper foil surface with sodium hydroxide solution after, being placed in vacuum degree is 1.0 × 10
-6torr, temperature are in the vacuum chamber of 100 DEG C dry 30 minutes, and Temperature fall, to room temperature, completes the processing procedure of Copper Foil;
Step 2: it is 1.0 × 10 that the Copper Foil after step 1 being processed is placed in vacuum degree
-6in the vacuum chamber of Torr, with the germanium target of three inch diameters and molybdenum target as germanium molybdenum alloy electrode, by high frequency magnetron sputter deposit Germanium and molybdenum on Copper Foil, sedimentation time is 1.5 hours; Make current known a kind of lithium ion battery Ge base negative material; The electrochemistry capacitance of this material is higher, reaches 1000mAh g
-1above, but i.e. very fast decay after circulation in 60 weeks.
Comparative example 2
18.36g citric acid and 3.41g cupric sulfate pentahydrate are dissolved in 50ml ethylene glycol, add 5.0g germanium dioxide, strong agitation; After dissolving completely, add ammoniacal liquor and regulate P
hfor 7.5-9.0; Solution is heated to 160 DEG C 3 hours, to promote citric acid and ethylene glycol heated polymerizable and the volatilization of unnecessary ethylene glycol; Product 160 DEG C of heating in vacuum to remove organic principle; Product under argon gas condition 750 DEG C heating three hours, make current known another kind of lithium ion battery Ge base negative material; This material capacity is greater than 750mAhg
-1decay is very fast, and within 50 weeks, loop attenuation is close to 30%.
In comparative example 1 and comparative example 2, electrode material also obtain high electrochemistry capacitance equally.But this type of method step is loaded down with trivial details, produce and amplify difficulty, cost is high.And the material capacity conservation rate of preparation is poor, in material in the cyclic test in 50-60 week, all there is the problem that capacity attenuation amplitude is large.
The preparation principle of material of the present invention:
The present invention adopts germanium oxide, material with carbon element to be raw material, and through the sintering processes of ball milling and 800-900 DEG C, coated through carbon thermal reduction, define the lithium ion battery germanium base negative material of germanium-graphite-carbon, the active material of its removal lithium embedded is mainly elemental Germanium; Carbon class material in presoma, can build regular carbon-coating structure in electrode material body interior and surface, improves the electric conductivity of material;
The method of ball milling-sinter bonded, effectively can either reduce the cost of manufacture of material, and the granularity of material can be made again to reach nano-scale, reduces the internal stress of material in electrochemical reaction, alleviates the trend of material efflorescence;
The present invention adopts germanium oxide as raw material, and under suitable heating temperature condition, while ensureing to form complete carbon clad structure, germanium oxide is reduced to germanium; The existence of charcoal clad structure, can to a great extent, weaken the tendency that germanium is reunited, and reduces its internal stress change in electrochemistry removal lithium embedded process, improve the overall cyclical stability of material.
Material charge/discharge capacity prepared by the present invention is high, good cycling stability, the making step of material is simple, effectively can improve the energy density of lithium ion battery, is applicable to the needs of large-scale commercial applications application, for high power, high-energy power consumption equipment, the development as electric motor car etc. provides the basis of development.
Although be described the preferred embodiments of the present invention above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not departing under the ambit that present inventive concept and claim protect, a lot of form can also be made.These all belong within protection scope of the present invention.
Claims (3)
1. the method for lithium ion battery germanium base negative material is prepared in carbon thermal reduction, it is characterized in that: comprise following preparation process:
Step 1: by weight ratio germanium dioxide: graphite: coal tar pitch=10:7:12, ball milling in ethanolic solution, heating detaches ethanolic solution, obtains the presoma of pitch, the coated germanium dioxide of graphite mixing charcoal;
Step 2: presoma step 1 made is placed in high temperature furnace, is warming up to 800-900 DEG C with the programming rate of 5 DEG C/min under argon gas atmosphere, sintering 5h, after Temperature fall cooling, namely forms carbon thermal reduction of the present invention and prepares lithium ion battery germanium base negative material.
2. the method for lithium ion battery germanium base negative material is prepared in carbon thermal reduction according to claim 1, it is characterized in that: the weight of described germanium dioxide, graphite, coal tar pitch and be 29g:100ml with the volume ratio of ethanol.
3. the method for lithium ion battery germanium base negative material is prepared in carbon thermal reduction according to claim 1, it is characterized in that: described Ball-milling Time is 60 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070891A (en) * | 2015-09-06 | 2015-11-18 | 福建师范大学 | Preparation of Ge/GeO2-mesoporous carbon composite electrode material for lithium ion battery and application of Ge/GeO2-mesoporous carbon composite electrode material |
| CN108281627A (en) * | 2018-01-03 | 2018-07-13 | 中国科学院上海硅酸盐研究所 | A kind of lithium ion battery germanium carbon compound cathode materials and preparation method thereof |
| CN109037652A (en) * | 2018-08-16 | 2018-12-18 | 福州大学 | A kind of preparation method and application of nitrogen-doped carbon cladding graduation germanium junction structure |
| CN110085847A (en) * | 2019-05-15 | 2019-08-02 | 中国人民解放军国防科技大学 | Germanium/carbon composite cathode material of lithium ion battery and preparation method and application thereof |
| CN110556525A (en) * | 2019-08-21 | 2019-12-10 | 华南理工大学 | lithium germanate, lithium germanate/graphite composite negative electrode material, preparation method thereof and application thereof in assembled lithium battery |
| CN115036505A (en) * | 2022-05-27 | 2022-09-09 | 江苏科技大学 | Carbon-coated germanium composite negative electrode material for lithium ion battery and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070891A (en) * | 2015-09-06 | 2015-11-18 | 福建师范大学 | Preparation of Ge/GeO2-mesoporous carbon composite electrode material for lithium ion battery and application of Ge/GeO2-mesoporous carbon composite electrode material |
| CN105070891B (en) * | 2015-09-06 | 2017-08-25 | 福建师范大学 | Lithium ion battery Ge/GeO2Mesoporous carbon composite electrode material is prepared and its applied |
| CN108281627A (en) * | 2018-01-03 | 2018-07-13 | 中国科学院上海硅酸盐研究所 | A kind of lithium ion battery germanium carbon compound cathode materials and preparation method thereof |
| CN108281627B (en) * | 2018-01-03 | 2021-05-25 | 中国科学院上海硅酸盐研究所 | Germanium-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN109037652A (en) * | 2018-08-16 | 2018-12-18 | 福州大学 | A kind of preparation method and application of nitrogen-doped carbon cladding graduation germanium junction structure |
| CN109037652B (en) * | 2018-08-16 | 2021-04-27 | 福州大学 | Preparation method and application of nitrogen-doped carbon-coated graded germanium structure |
| CN110085847A (en) * | 2019-05-15 | 2019-08-02 | 中国人民解放军国防科技大学 | Germanium/carbon composite cathode material of lithium ion battery and preparation method and application thereof |
| CN110556525A (en) * | 2019-08-21 | 2019-12-10 | 华南理工大学 | lithium germanate, lithium germanate/graphite composite negative electrode material, preparation method thereof and application thereof in assembled lithium battery |
| CN110556525B (en) * | 2019-08-21 | 2022-03-29 | 华南理工大学 | Lithium germanate, lithium germanate/graphite composite negative electrode material, preparation method thereof and application thereof in assembled lithium battery |
| CN115036505A (en) * | 2022-05-27 | 2022-09-09 | 江苏科技大学 | Carbon-coated germanium composite negative electrode material for lithium ion battery and preparation method and application thereof |
| CN115036505B (en) * | 2022-05-27 | 2023-09-29 | 江苏科技大学 | Carbon-coated germanium composite anode material for lithium ion battery and preparation method and application thereof |
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