CN105244502A - Method for preparing anode material of lithium ion battery by high-temperature reaction of expansible graphite and zinc powder - Google Patents
Method for preparing anode material of lithium ion battery by high-temperature reaction of expansible graphite and zinc powder Download PDFInfo
- Publication number
- CN105244502A CN105244502A CN201510543453.3A CN201510543453A CN105244502A CN 105244502 A CN105244502 A CN 105244502A CN 201510543453 A CN201510543453 A CN 201510543453A CN 105244502 A CN105244502 A CN 105244502A
- Authority
- CN
- China
- Prior art keywords
- graphite
- zinc powder
- expansible graphite
- zinc
- expanded graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M4/58—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
-
- 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
-
- 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
-
- 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 an anode material of a lithium ion battery by high-temperature reaction of expansible graphite and zinc powder. The method comprises the following steps of using the expansible graphite and the zinc powder as raw materials; carrying out high-temperature reaction of the expansible graphite and the zinc powder in a temperature condition of the zinc powder serving as an air phase; and preparing to obtain a composite electrode material of the expanded graphite and zinc oxide, wherein a vacuum environment is controlled or an inert gas is introduced during the reaction process. The method disclosed by the invention is a one-step reaction method, the problems of complicated step and long time consumption existing in the prior art by using the expanded graphite and a zinc source for wet synthesis are solved, and the preparation process is simplified; not only the zinc oxide is deposited on the surface of the expanded graphite and among layers, but also the oxidation-reduction reactions are included; and a part of oxygen in the expanded graphite is reduced by zinc, the oxidation degree of the expanded graphite is further reduced, meanwhile, the generated zinc oxide is taken as the electrode material, and the specific capacity of the electrode material is also improved.
Description
Technical field
The present invention relates to the preparation field of lithium ion battery negative material, be specifically related to a kind of method being prepared lithium ion battery negative material by expansible graphite and zinc powder pyroreaction.
Background technology
Lithium ion battery has more and more been applied in the instrument such as electric motor car, mobile phone, become energy storage instrument important in people's life, people are also more and more higher for the requirement of lithium ion battery, and the key improving performance of lithium ion battery is improve and invent new electrode material.
Graphite is a kind of natural resources of rich reserves, is conventional lithium ion battery electrode material.Graphite is a kind of layer structure, and on same layer, carbon carbon atom connects with covalent bond, is that a kind of π key connects between layers.Combination is between layers more weak.And expansible graphite be exactly crystalline flake graphite through the strong oxidizer process such as process such as red fuming nitric acid (RFNA), potassium permanganate, through a kind of graphite oxide that the steps such as super-dry cleaning obtain.The expanded graphite obtained through pyroreaction just has very large specific area and some oxygen-containing functional groups.Expanded graphite can be used as encapsulant, Adsorption of Organic material, substitute normal gauze make medical dressing and battery electrode material etc.Expanded graphite is owing to being a kind of oxidizability graphite, and conductivity is poorer than graphite, and it is lower that independent expanded graphite does electrode material specific capacity, but its layer structure is opened, and surface area obviously increases, the embedding and the deintercalation preparation that are applicable to lithium ion are simple, cheap, be a kind of electrode material preferably.
Zinc oxide is a kind of transition metal oxide, theoretical specific capacity is up to 978mAh/g, be a kind of cell negative electrode material be widely studied, but the poorly conductive of zinc oxide itself is difficult to the height ratio capacity giving full play to itself, so Material cladding that is normal and good conductivity prepares electrode material.
Prior art discloses the method (as CN103215628A, CN102580715A etc.) that some utilize expanded graphite and zinc source Moist chemical synthesis expanded graphite and zinc oxide composite, but obtained material will through repeatedly washing and dry run, step more complicated; In addition, based on the consideration of electrode material, also useful Graphene replaces the method for the composite material of both expanded graphite Moist chemical synthesis, but Graphene preparation process is complicated, and price is high, is not suitable for large-scale application; Further, prior art is prepared in the method for expanded graphite and zinc oxide composite, and the expanded graphite used still exists the problem that electrode material specific capacity is low and degree of oxidation is slightly high.
Summary of the invention
For solving above-mentioned problems of the prior art, the invention provides the method that expanded graphite and zinc oxide combination electrode material are prepared in the reaction of a kind of one-step method.
Consider the step complexity of existing expanded graphite and zinc oxide composite preparation technology, (boiling point is at about 902 DEG C to still have the characteristic of reducible space and zinc simple substance self in conjunction with expanded graphite degree of oxidation, and high temperature has certain reproducibility), inventor is found by research, under the high temperature conditions, zinc powder becomes gas phase, and what utilize expanded graphite enriches Manzo gap structure and good adsorption properties, by zinc gas phase diffusion in the synusia of expanded graphite; And the reproducibility of zinc under utilizing hot conditions, reduces the oxygen in conjunction with expanded graphite; Further, the zinc oxide dispersed deposition of reaction, in expanded graphite, improves the specific capacity of expanded graphite.
Concrete, the present invention relates to following technical scheme:
A kind of method preparing expanded graphite and zinc oxide combination electrode material, expansible graphite and zinc powder is used to be raw material, it is characterized in that, by expansible graphite and zinc powder mixing, be carry out pyroreaction under the temperature conditions of gas phase at zinc powder, prepare expanded graphite and zinc oxide combination electrode material, course of reaction controls vacuum environment or passes into inert gas.
Preferably, in described method, expansible graphite is ground, obtain relatively fine particle, then expansible graphite and zinc powder are mixed by certain mass ratio.
Preferably, in described method, the mass ratio of expansible graphite and zinc powder is 1:2.5 ~ 6.
Preferably, in described method, first at high temperature by expansible graphite expansion process, then it is mixed with zinc.
Preferably, become this 2 point of expansion characteristics of gas phase, expansible graphite expansion based on zinc powder, the designing requirement of reaction temperature is between 900 DEG C to 1100 DEG C.
Preferably, in described method, pyroreaction, by diamond heating, also can replace with the stove of the environment and high temperature that can provide high vacuum environment or be full of argon gas; More preferred, the method that wind-force can be adopted to advertise, makes raw material fully react.
Preferably, in described method, the material prepared ball milling in ball mill, obtains levigate material.
Preferably, the invention provides a kind of method preparing expanded graphite and zinc oxide combination electrode material, comprise the steps, (1) by expansible graphite mortar grinder, obtain thinner particle, then weighing expansible graphite and zinc powder mixed by certain mass ratio and use mortar grinder, mixing; (2) diamond heating is arranged insulation a period of time to a certain temperature of more than 900 DEG C, logical high-purity argon gas, eliminates air in tube; (3) ground sample is put into the quartz glass bottle of band stopper, and be connected and fixed stopper and body with iron wire, dry a period of time in an oven; (4) tube furnace being full of argon gas put into by quartz glass bottle obtained in the previous step, insulation a period of time, takes out bottle, is cooled to room temperature, takes out sample, obtains prepared material; (5) by material obtained above ball milling in ball mill, levigate material is obtained.
Wherein preferred, step (1) mortar used is agate mortar;
Preferably, the granular size of expansible graphite of step (1) expansible graphite milling time depending on obtaining, general milling time need more than 30 minutes;
The mass ratio of step (1) expansible graphite and zinc powder is 1:2.5 ~ 6.
The designing requirement of step (2) reaction temperature based on the fusing point of zinc powder, this 2 point of expansion characteristics that expansible graphite expands, the arbitrary temperature preferably between 900 DEG C to 950 DEG C.
The time of step (2) tube furnace logical argon gas before step (3) should be determined according to the speed of the volume size of tube furnace and logical argon gas, at least will more than 20 minutes.
In step (2), tube furnace used also can replace with the stove of the environment and high temperature that can provide high vacuum environment or be full of argon gas.When reacting in above-mentioned stove, the method that wind-force can be adopted to advertise, makes raw material fully react.In addition also first at high temperature by expansible graphite expansion process, then by material and zinc ground and mixed, the reaction of step (3) can be carried out, then take out material and carry out ball-milling treatment.
Step (3) oven temperature is arranged between 60 ~ 80 DEG C, 1 hour time.
In step (4), temperature retention time is arranged between 20 minutes to 60 minutes.
Step (5) balls mill speed 1400r/min, every spheroidal graphite stops 20 minutes in 30 minutes, at least so repeats 4 times.
The present invention achieves following useful effect:
(1) the method for the invention is single step reaction method, which overcomes in prior art to utilize that expanded graphite and the step existing for the Moist chemical synthesis of zinc source are complicated, the problem of length consuming time, simplifies step of preparation process;
(2) the method for the invention, be not only zinc oxide in the deposition of expanded graphite surface and interlayer, also comprise redox reaction, the oxygen in reduction swellability graphite is carried out by zinc, further reduction expanded graphite degree of oxidation (as Fig. 5), the zinc oxide simultaneously generated, as electrode material, turn improves the specific capacity of electrode material.
(3) by charge-discharge test, electrode material prepared by the method for the invention has good specific capacity and cycle performance.
The present invention improves the problem that expanded graphite is low as electrode material specific capacity and degree of oxidation is high, prepare expanded graphite and zinc oxide composite by the simple method of one, obtain a kind of can extensive use, the lithium ion battery electrode material of cheap and large-scale production.
Accompanying drawing explanation
Fig. 1: the SEM image of expansible graphite.
Fig. 2: the EDS power spectrum of expansible graphite.
The SEM image under different amplification of the expanded graphite obtained after Fig. 3: 900 DEG C of high-temperature expansions.
Fig. 4: the SEM when SEM figure and (b) 5000 times when the EG/ZnO (a) 1000 times that example 1 obtains amplifies amplifies schemes.
The EDS of Fig. 5: the EG/ZnO that example 1 is obtained can spectrogram.
The EDS maps constituent analysis of Fig. 6: the EG/ZnO that example 1 is obtained.
Fig. 7: electrode material EG/ZnO (a) first three circle charging and discharging curve and (b) cycle performance curve under 100mA/g that example 1 is obtained.
Fig. 8: expanded graphite does charging and discharging curve and (b) cycle performance curve of first three circle of (a) of electrode material under 100mA/g.
Embodiment
Below in conjunction with specific embodiment, the invention will be further elaborated.Particularly point out at this, following embodiment used is only not used in restriction range of application of the present invention for illustration of the present invention.
Embodiment 1: the expansible graphite that experiment uses is the raw material for the preparation of encapsulant that enterprise's routine provides, and the purity of zinc powder is 99.0%.With deionized water and washes of absolute alcohol experimental facilities.
Expansible graphite agate mortar is ground 30 minutes, obtains thinner particle, then will weigh expansible graphite 0.25g and zinc powder 1.5g and mix and with agate mortar grinding, mix.By diamond heating to 950 DEG C, arrange insulation 1 hour, during experiment, when displays temperature is about to be increased to 950 DEG C, logical 20 minutes high-purity argon gas, eliminate air in tube.Ground sample is put into the quartz glass bottle of band stopper, and be connected and fixed stopper and body with iron wire, dry 1 hour in the baking oven of 60 DEG C.The 950 DEG C of tube furnaces being full of argon gas put into by quartz glass bottle obtained in the previous step, are incubated 30 minutes, take out bottle, be cooled to room temperature, take out sample, obtain prepared material (EG/ZnO).By material obtained above ball milling in ball mill, balls mill speed 1400r/min, every spheroidal graphite stops 20 minutes in 30 minutes, so repeats to obtain levigate material 6 times.
Embodiment 2: the expansible graphite that experiment uses is the raw material for the preparation of encapsulant that enterprise's routine provides, and the purity of zinc powder is 99.0%.With deionized water and washes of absolute alcohol experimental facilities.
Expansible graphite agate mortar is ground 30 minutes, obtains thinner particle, then will weigh expansible graphite 0.3g and zinc powder 0.75g and mix and with agate mortar grinding, mix.By diamond heating to 930 DEG C, arrange insulation 1 hour, during experiment, when displays temperature is about to be increased to 930 DEG C, logical 20 minutes high-purity argon gas, eliminate air in tube.Ground sample is put into the quartz glass bottle of band stopper, and be connected and fixed stopper and body with iron wire, dry 1 hour in the baking oven of 60 DEG C.The tube furnace being full of argon gas put into by quartz glass bottle obtained in the previous step, is incubated 20 minutes, takes out bottle, be cooled to room temperature, takes out sample, obtains prepared material (EG/ZnO).By material obtained above ball milling in ball mill, balls mill speed 1400r/min, every spheroidal graphite stops 20 minutes in 30 minutes, so repeats to obtain levigate material 6 times.
Embodiment 3: the expansible graphite that experiment uses is the raw material for the preparation of encapsulant that enterprise's routine provides, and the purity of zinc powder is 99.0%.With deionized water and washes of absolute alcohol experimental facilities.
By expansible graphite mortar grinder 30 minutes, obtain thinner particle, then will weigh expansible graphite 0.4g.Diamond heating is arranged insulation 30 minutes to 910 DEG C, and when being about to be increased to 910 DEG C, logical 20 minutes high-purity argon gas, eliminate air in tube.Ground expansible graphite is put into the quartz glass bottle of band stopper, and be connected and fixed stopper and body with iron wire, dry 1 hour in the baking oven of 60 DEG C.The tube furnace being full of argon gas put into by quartz glass bottle obtained in the previous step, is incubated 5 minutes, takes out bottle, be cooled to room temperature, obtain expanded graphite.Zinc powder and expanded graphite are weighed 0.75g and 0.3g respectively, puts into quartz glass bottle, be stoppered stopper, with iron wire by body and stopper tighten, fully rock, zinc contacted with expanded graphite evenly, quartz glass bottle is put into temperature be 60 DEG C baking oven dry 1 hour.Diamond heating is arranged insulation 1 hour to 930 DEG C, and when being about to be increased to 930 DEG C, logical 20 minutes high-purity argon gas, eliminate air in tube.The tube furnace being full of argon gas put into by the quartz glass bottle taking out baking, is incubated 20 minutes, takes out bottle, be cooled to room temperature, takes out material.Material obtained above is put into ball mill ball milling, ball milling balls mill speed 1400r/min, every spheroidal graphite stops 20 minutes in 30 minutes, so repeats to obtain levigate material 6 times.
Embodiment 4: material property detect and characterize: the material scanning electron microscopy (SEM) prepared by the present invention observes microstructure, with SEM with energy disperse spectroscopy (EDS) analyze contained element and Elemental redistribution.The performance of material, by material is made half-cell, carries out charge-discharge test, the specific capacity of Knowing material and cycle performance.
Embodiment 5: the preparation method of lithium ion battery half-cell: obtained electrode material and polyvinylidene fluoride (PVDF), carbon black are mixed according to the ratio of mass ratio 8:1:1, with 1-METHYLPYRROLIDONE (NMP) as solvent, obtained slurry, be coated on Copper Foil, thickness 20 μm, vacuum drying at 70 DEG C, general insulation 10 hours.With tabletting machine, obtain the cathode pole piece that diameter is 12mm, using lithium metal as negative pole, microporous polypropylene membrane as barrier film, lithium hexafluoro phosphate (LiPF
6) (EC/DEC=1:1 volume ratio) as electrolyte.Assembled battery in the glove box being full of argon gas, after shelving 12 hours, be placed on new prestige battery test system and carry out constant current charge-discharge test, current density is 100mA/g, and voltage range is 0.1V-3.0V.
Found through experiments, preparation-obtained electrode material is obviously better than the performance of expanded graphite electrode material, and reaches the performance (see Fig. 7, Fig. 8) of expanded graphite that prior art additive method prepares and zinc oxide composite.
Claims (10)
1. prepare the method for expanded graphite and zinc oxide combination electrode material for one kind, expansible graphite and zinc powder is used to be raw material, it is characterized in that, by expansible graphite and zinc powder mixing, be carry out pyroreaction under the temperature conditions of gas phase at zinc powder, prepare expanded graphite and zinc oxide combination electrode material, course of reaction controls vacuum environment or passes into inert gas.
2. method according to claim 1, is characterized in that, ground by expansible graphite, obtain relatively fine particle, then expansible graphite and zinc powder are mixed by certain mass ratio.
3. method according to claim 1, it is characterized in that, the mass ratio of expansible graphite and zinc powder is 1:2.5 ~ 6.
4. method according to claim 1, is characterized in that, first at high temperature by expansible graphite expansion process before reaction, then it mixed with zinc powder.
5. method according to claim 1, it is characterized in that, reaction temperature is between 900 DEG C to 1100 DEG C.
6. method according to claim 1, is characterized in that, pyroreaction by diamond heating, or uses and provides high vacuum environment or be full of the environment of argon gas and other stoves of high temperature.
7. method according to claim 1, is characterized in that, adopt the method that wind-force is advertised in course of reaction, raw material is fully reacted.
8. method according to claim 1, it is characterized in that, the material prepared ball milling in ball mill, obtains levigate material.
9. method according to claim 8, is characterized in that, balls mill speed 1400r/min, and every spheroidal graphite stops 20 minutes in 30 minutes, at least so repeats 4 times.
10. the method according to any one of claim 1-9, is characterized in that, comprises the steps, (1) by expansible graphite mortar grinder, obtain thinner particle, then weighing expansible graphite and zinc powder mixed by certain mass ratio and use mortar grinder, mixing; (2) diamond heating is arranged insulation a period of time to a certain temperature of more than 900 DEG C, logical high-purity argon gas, eliminates air in tube; (3) ground sample is put into the quartz glass bottle of band stopper, and be connected and fixed stopper and body with iron wire, dry a period of time in an oven; (4) tube furnace being full of argon gas put into by quartz glass bottle obtained in the previous step, the insulation reaction time, takes out bottle, is cooled to room temperature, takes out sample, obtains prepared material; (5) by material obtained above ball milling in ball mill, levigate material is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510543453.3A CN105244502B (en) | 2015-08-28 | 2015-08-28 | A kind of method that lithium ion battery negative material is prepared by expansible graphite and zinc powder pyroreaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510543453.3A CN105244502B (en) | 2015-08-28 | 2015-08-28 | A kind of method that lithium ion battery negative material is prepared by expansible graphite and zinc powder pyroreaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105244502A true CN105244502A (en) | 2016-01-13 |
| CN105244502B CN105244502B (en) | 2017-10-17 |
Family
ID=55042061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510543453.3A Active CN105244502B (en) | 2015-08-28 | 2015-08-28 | A kind of method that lithium ion battery negative material is prepared by expansible graphite and zinc powder pyroreaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105244502B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106340626A (en) * | 2016-10-05 | 2017-01-18 | 复旦大学 | High-capacity lithium-stored oxide nano-film composite expanded graphite material and preparation method thereof |
| CN107381557A (en) * | 2017-08-16 | 2017-11-24 | 厦门信果石墨烯科技有限公司 | A kind of preparation method for mass producing graphene |
| CN110495023A (en) * | 2017-04-13 | 2019-11-22 | 埃卡特有限公司 | The removing graphite composite material of ZnO nano particle coating, the preparation method of the composite material and its application in Li-ion batteries piles |
| CN114497476A (en) * | 2021-12-24 | 2022-05-13 | 合肥国轩高科动力能源有限公司 | Expanded graphite nano-silicon composite negative electrode material for lithium ion battery and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157315A (en) * | 2011-03-21 | 2011-08-17 | 福州大学 | Emitting cathode based on composite material of graphene/zinc oxide nanowire and preparation of same |
| CN102580715A (en) * | 2012-01-10 | 2012-07-18 | 黑龙江大学 | Method for preparing zinc oxide/graphene composite from expanded graphite by stripping |
| CN103215628A (en) * | 2013-04-17 | 2013-07-24 | 中国石油大学(华东) | Method for electro-chemical compounding of graphene and metallic oxide |
-
2015
- 2015-08-28 CN CN201510543453.3A patent/CN105244502B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157315A (en) * | 2011-03-21 | 2011-08-17 | 福州大学 | Emitting cathode based on composite material of graphene/zinc oxide nanowire and preparation of same |
| CN102580715A (en) * | 2012-01-10 | 2012-07-18 | 黑龙江大学 | Method for preparing zinc oxide/graphene composite from expanded graphite by stripping |
| CN103215628A (en) * | 2013-04-17 | 2013-07-24 | 中国石油大学(华东) | Method for electro-chemical compounding of graphene and metallic oxide |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106340626A (en) * | 2016-10-05 | 2017-01-18 | 复旦大学 | High-capacity lithium-stored oxide nano-film composite expanded graphite material and preparation method thereof |
| CN110495023A (en) * | 2017-04-13 | 2019-11-22 | 埃卡特有限公司 | The removing graphite composite material of ZnO nano particle coating, the preparation method of the composite material and its application in Li-ion batteries piles |
| US11594723B2 (en) | 2017-04-13 | 2023-02-28 | Eckart Gmbh | ZnO nanoparticle coated exfoliated graphite composite, method of producing composite and use in Li-ion battery |
| CN107381557A (en) * | 2017-08-16 | 2017-11-24 | 厦门信果石墨烯科技有限公司 | A kind of preparation method for mass producing graphene |
| CN114497476A (en) * | 2021-12-24 | 2022-05-13 | 合肥国轩高科动力能源有限公司 | Expanded graphite nano-silicon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN114497476B (en) * | 2021-12-24 | 2023-08-04 | 合肥国轩高科动力能源有限公司 | Expanded graphite nano-silicon composite anode material for lithium ion battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105244502B (en) | 2017-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103367719B (en) | The preparation method of Yolk-shell structure tin dioxide-nitrogen-dopcarbon carbon material | |
| CN109286012B (en) | Preparation method of high-rate silica-based lithium battery negative electrode material | |
| CN103730644B (en) | Silicon-silicon oxide-carbon composite negative pole material of lithium ion battery preparation method | |
| CN102969489B (en) | A kind of Si-C composite material and preparation method thereof, lithium ion battery containing this material | |
| CN102306759B (en) | Silicon monoxide composite cathode material for lithium ion battery, and preparation method thereof | |
| CN102169985B (en) | Preparation method of lithium ion battery carbon anode material | |
| CN104009210B (en) | A kind of porous silicon/carbon composite material, Preparation method and use | |
| CN104934608A (en) | Preparation method of in-situ graphene coated lithium ion battery cathode material | |
| CN103035917A (en) | Preparation method of silicon dioxide/ carbon composite negative electrode material for lithium ion battery | |
| CN101969112A (en) | Anode material and cathode material for lithium ion battery and modifying method thereof | |
| CN103022435B (en) | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof | |
| CN102983317A (en) | Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery | |
| CN109698326A (en) | A kind of organic phosphorization tin/oxidized graphite composite material for sodium-ion battery cathode | |
| CN103094551B (en) | A kind of graphite/manganous oxide combination electrode material and preparation method thereof | |
| CN105244502A (en) | Method for preparing anode material of lithium ion battery by high-temperature reaction of expansible graphite and zinc powder | |
| CN103618065B (en) | LiFePO 4 material and preparation method thereof | |
| CN103972508B (en) | A kind of inorganic doping/coating modification native graphite, preparation method and application thereof | |
| CN107240685B (en) | Iron trifluoride/lithium hexafluoroferrate composite positive electrode material, preparation and application thereof | |
| CN103996823B (en) | A kind of rapid microwave reaction method for preparing of power lithium-ion battery ternary polyanion phosphate/carbon positive electrode | |
| CN103545492B (en) | The preparation method of the multiple composite anode material of lithium ion battery | |
| CN104466182A (en) | Nitrogen-doped nanocarbon coated/oxidized modified graphite composite material and preparation method thereof | |
| CN103378355A (en) | Alkali metal secondary battery as well as negative active substance, negative material and negative electrode thereof, and preparation method of negative active substance | |
| CN103199248B (en) | The preparation method of the coated niobium doped iron lithium phosphate of carbon-cobalt acid lithium composite positive pole | |
| CN102683702B (en) | Preparation method of lithium iron phosphate with surface being uniformly coated by carbon | |
| CN107316974A (en) | A kind of preparation method of Nano Silver composite lithium iron phosphate cathode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |