CN106784700B - Multilayer silicon/graphene composite lithium battery cathode material and preparation method thereof - Google Patents
Multilayer silicon/graphene composite lithium battery cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN106784700B CN106784700B CN201611222585.7A CN201611222585A CN106784700B CN 106784700 B CN106784700 B CN 106784700B CN 201611222585 A CN201611222585 A CN 201611222585A CN 106784700 B CN106784700 B CN 106784700B
- Authority
- CN
- China
- Prior art keywords
- silicon
- graphene
- lithium battery
- foamed nickel
- composite lithium
- 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.)
- Active
Links
Images
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/625—Carbon or graphite
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 belongs to the technical field of energy materials, and provides a multilayer silicon/graphene composite lithium battery cathode material of a nickel foam collector and a preparation method thereof, which are used for overcoming the defects that a silicon cathode has a violent volume effect and is difficult to form a stable surface solid electrolyte membrane in the electrochemical lithium storage process, and the electrical cycle performance of the solid electrolyte membrane is poor due to low intrinsic conductivity of the solid electrolyte membrane; the multi-layer silicon/graphene composite lithium battery cathode material comprises foamed nickel, graphene layers and silicon layers, wherein the graphene layers and the silicon layers are sequentially and alternately arranged on the foamed nickel, and the graphene layer is arranged on the topmost layer; a multilayer graphene/silicon/graphene sandwich structure is formed, silicon powder is wrapped in a layered mode by utilizing the high mechanical property and high conductivity of graphene, and the volume of silicon powder is effectively inhibited from changing greatly in the charging and discharging process, so that a stable SEI (solid electrolyte interphase) film is formed, and the rate characteristic and the cycling stability are improved on the premise of keeping the high specific capacity of silicon; meanwhile, the preparation method has the advantages of simple process, low cost and good repeatability.
Description
Technical Field
The invention belongs to the technical field of energy materials, relates to a lithium battery negative electrode material and a preparation method thereof, and particularly relates to a multilayer silicon/graphene composite lithium battery negative electrode material of a foamed nickel collector and a preparation method thereof.
Background
The development of green energy technology and low-carbon economy puts higher and higher requirements on next-generation high-performance lithium ion batteries, and in the aspect of negative electrode materials, the current commercial lithium ion batteries mainly adopt graphite carbon negative electrode materials; however, the theoretical specific capacity of graphite is only 372mAh g-1Moreover, the lithium-embedded potential platform is close to metal lithium, and the phenomenon of lithium precipitation is easy to occur during rapid charging or low-temperature charging, so that potential safety hazards are caused; therefore, the development of high-energy power lithium ion batteries urgently needs to seek high-capacity, long-cycle and safeThe novel reliable anode material replaces a graphite carbon anode.
Among various negative electrode materials, silicon attracts more and more researchers' attention with its obvious advantages and potentials, and the theoretical lithium storage capacity of silicon is up to 4200mAh g-1The capacity of the graphite is more than 10 times, and the capacity is the highest among elements capable of alloying to store lithium; the voltage platform of silicon is slightly higher than that of graphite, so that the phenomenon of lithium precipitation on the surface is difficult to cause during charging, and the safety performance of the silicon is better than that of a graphite cathode material; in addition, silicon is one of the elements with the highest abundance in the earth crust, has wide sources and low price, and is suitable for industrial production; however, silicon still has many problems as the negative electrode of the next generation lithium ion battery: firstly, in the electrochemical lithium storage process, silicon atoms are combined with lithium atoms to obtain Li4.4The volume expansion change of the material of the silicon alloy phase reaches more than 300 percent, the mechanical acting force generated by the huge volume effect can gradually separate the electrode active substance from the current collector and the silicon active phase can also be pulverized, so that the electrical contact with the current collector is lost, and the cycle performance of the electrode is rapidly reduced; secondly, silicon itself is a semiconductor material with low intrinsic conductivity of only 6.7.10-4S·cm-1A conductive agent is added to improve the electronic conductivity of the electrode; third, LiPF in existing electrolyte6The decomposition generates trace HF to corrode silicon, which causes the capacity of the silicon-based negative electrode to be attenuated, and the silicon is subjected to the conventional LiPF due to the violent volume effect6It is difficult to form a stable surface Solid Electrolyte Interface (SEI) film in the electrolyte, and a new SEI film is continuously formed on a newly exposed silicon surface along with the destruction of an electrode structure, resulting in a decrease in charge and discharge efficiency and an increase in capacity fading.
Based on this, overcoming the above drawbacks has become a focus of research in the present invention.
Disclosure of Invention
The invention aims to overcome the defects of the silicon cathode and provides a multilayer silicon/graphene composite lithium battery cathode material of a foam nickel collector electrode and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a multilayer silicon/graphene composite lithium battery cathode material comprises foamed nickel, graphene layers and silicon layers, wherein the graphene layers and the silicon layers are sequentially and alternately arranged on the foamed nickel, and the graphene layer is arranged on the topmost layer; wherein the number of the silicon layers is n, n is more than or equal to 1 and less than or equal to 20, and the number of the graphene layers is n + 1.
Further, the preparation method of the multilayer silicon/graphene composite lithium battery anode material comprises the following steps:
step 1, pressing foamed nickel into a wafer, and cleaning for later use;
step 3, cleaning the nano silicon, and then adding the nano silicon into absolute ethyl alcohol: preparing a silicon dispersion solution with the concentration of 1-5M in a mixed solution of 9:1 ethylene glycol;
step 4, soaking the foamed nickel into the graphene oxide solution, taking out the foamed nickel, and drying the foamed nickel in an inert atmosphere at the temperature of 60-90 ℃ for 10-15 min;
step 5, soaking the foamed nickel treated in the step 4 into a silicon dispersion solution, taking out and drying in an inert atmosphere at the temperature of 60-90 ℃ for 5-10 min;
step 6, repeating the steps 4 to 5 to prepare the silicon/graphene composite lithium battery cathode material with n silicon layers and n being more than or equal to 1 and less than or equal to 20;
step 7, pressing the silicon/graphene composite negative electrode material prepared in the step 6 into a sheet at 8-10 Mpa by using a tablet press;
and 8, putting the sheet into a vacuum tube furnace, and reducing graphene oxide at 550-650 ℃ in an inert atmosphere to obtain the foamed nickel collector electrode multilayer silicon/graphene composite lithium battery negative electrode material.
Furthermore, the cleaning process of the foamed nickel in the step 1 is as follows: preparing a 4-6M hydrochloric acid solution, adding foamed nickel pressed into a wafer into the hydrochloric acid solution, ultrasonically cleaning for 10-20min, and then cleaning with absolute ethyl alcohol.
The cleaning process of the nano silicon in the step 3 comprises the following steps: dropping HF into absolute ethyl alcohol: deionized water 1: 1, preparing 4-6M HF solution; and then adding the nano silicon into an HF solution, carrying out ultrasonic cleaning for 10-20min, and then centrifuging or carrying out suction filtration.
The heat treatment process of the vacuum tube furnace in the step 8 comprises the following steps: the temperature rise speed is 5 ℃/min, the temperature is raised to 550-650 ℃, and the temperature is kept for 2 h.
The inert gas in the steps 1-8 comprises all common inert gases, such as nitrogen, argon and the like.
The invention has the beneficial effects that:
the invention provides a multilayer silicon/graphene composite lithium battery cathode material of a foamed nickel collector electrode, which adopts a multilayer silicon/graphene alternating structure to form a multilayer graphene/silicon/graphene sandwich structure, and silicon powder is coated in a layered manner by utilizing the high mechanical property and high conductivity of graphene, so that the volume of silicon powder in the charging and discharging process is effectively inhibited from changing greatly, a stable SEI film is formed conveniently, and the multiplying power characteristic and the cycling stability are improved on the premise of keeping the high specific capacity of silicon; the negative electrode material of the multilayer silicon/graphene composite lithium battery is 3 A.g-1The charge and discharge cycle under the current is 500 circles, and the cycle retention rate still exceeds 60 percent; at 0.2, 0.4, 1, 2, 4, 8, 16 A.g-1The corresponding specific capacities are respectively 2190, 1920, 1715, 1520, 1270 and 960 mAh.g under the change of the charging and discharging currents of the steps-1(ii) a The lithium ion battery cathode has high current charge and discharge capacity and good cycle charge and discharge performance, and can meet the application of the next generation lithium ion battery cathode. Meanwhile, the preparation method of the multilayer silicon/graphene composite lithium battery cathode material has the advantages of simple process, low cost and good repeatability; the prepared multilayer silicon/graphene composite lithium battery cathode material has high current charge and discharge capacity and good cycle charge and discharge performance.
Drawings
Fig. 1 is an XRD diffraction spectrum of the 5-layer silicon/graphene composite anode material in example.
Fig. 2 is a Raman spectrum of the 5-layer silicon/graphene composite anode material in the example.
Fig. 3 is a graph of 500 cycles of specific capacity of the 5-layer silicon/graphene composite anode material in the example.
Fig. 4 is a graph of the rate cycle specific capacity of the 5-layer silicon/graphene composite negative electrode material in the example.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples, but the embodiments of the present invention are not limited thereto.
Example 1
The embodiment provides a 5-layer nickel foam collector silicon/graphene composite lithium battery cathode material, which comprises the following steps:
step 1, foam nickel pretreatment: preparing a 4M hydrochloric acid solution, adding the foamed nickel pressed into a wafer into the hydrochloric acid solution, ultrasonically cleaning for 20min, and then cleaning with absolute ethyl alcohol;
step 3, dropping HF into absolute ethyl alcohol in volume ratio: deionized water 1: 1, preparing a 5M HF solution; then adding the nano silicon into an HF solution, carrying out ultrasonic cleaning for 20min, and then centrifuging or carrying out suction filtration; adding the cleaned nano silicon into absolute ethyl alcohol: preparing a silicon dispersion solution with the concentration of 1M in a mixed solution of 9:1 ethylene glycol;
step 4, soaking the foamed nickel (completely immersed in the solution and then pulled and taken out) into the graphene oxide solution, taking out and drying in an inert atmosphere at 80 ℃ for 15 min;
step 5, soaking the foamed nickel into the silicon solution, taking out the foamed nickel, and drying the foamed nickel for 10min in an inert atmosphere at the temperature of 80 ℃;
step 6, repeating the steps 4 and 5, and preparing the composite lithium battery cathode material with 5 layers of 2 silicon layers and 3 graphene layers;
step 7, pressing the multilayer silicon/graphene oxide composite lithium battery cathode material with foamed nickel as a collector into a sheet on a tablet press at 10 Mpa;
step 8, placing the composite electrode slice into a vacuum tube furnace, and reducing graphene oxide at 600 ℃ in an inert atmosphere to obtain a foamed nickel collector electrode multilayer silicon/graphene composite lithium battery negative electrode material; wherein the heating rate of the heat treatment is 5 ℃/min, the temperature is raised to 600 ℃, and the heat is preserved for 2 h.
The structure and the electrical properties of the 5-layer foam nickel collector silicon/graphene composite lithium battery cathode material prepared by the method are characterized and tested, and the results are as follows:
1. structural characteristics
As shown in fig. 1, three strong peaks (110), (220), and (310) in XRD of the 5-layer silicon/graphene composite negative electrode are consistent with the pattern of silicon; broadening of the (002) peak of graphite occurs at 26 °, due to the diffraction peak broadening effect caused by the thin graphene layers; indicating that silicon and graphene coexist in the composite structure.
As shown in FIG. 2, the Raman spectrum of the 5-layer silicon/graphene composite negative electrode is 513cm-1A fine and high strong peak is corresponding to the silicon nano material; at 1305cm-1The D peak corresponding to graphene, which is the peak due to dispersion and defects; at 1590cm-1G peak corresponding to graphene, which is sp2A vibrational peak with carbon atoms bonded; the intensity of the D peak is obviously stronger than that of the G peak, which indicates that the graphene oxide is reduced into graphene.
2. Electrical properties
As shown in fig. 3, the 5-layer silicon/graphene composite negative electrode has good cycle characteristics at 3A · g-1The circulation retention rate of 60 percent is still kept after the current is circulated for 500 circles. As shown in FIG. 4, the specific capacity at different current rates is plotted at 0.2, 0.4, 1, 2, 4, 8, 16 A.g-1At the current rate, the corresponding specific capacities are 2190, 1920, 1715, 1520, 1270 and 960 mAh.g-1(ii) a Can satisfy heavy current charge and discharge, and has good rate characteristic.
Example 2
The 3-layer, 7-layer, 9-layer and 11-layer silicon/graphene composite lithium battery cathode materials are prepared by adopting the same process as in example 1, and the structural and electrical properties of the silicon/graphene composite lithium battery cathode materials are characterized and the test results of the silicon/graphene composite lithium battery cathode materials are the same as those of example 1.
In a word, through the material structure design, the silicon nano powder is wrapped in the layered graphene, so that the volume change of silicon in the charge and discharge process cannot influence the cycle effect, and a stable SEI film is formed; the preparation method is a simple, practical and effective preparation method of the high-performance silicon composite cathode, and can realize the application of commercial lithium ion batteries of silicon.
While the invention has been described with reference to specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise; all of the disclosed features, or all of the method or process steps, may be combined in any combination, except mutually exclusive features and/or steps.
Claims (3)
1. A preparation method of a multilayer silicon/graphene composite lithium battery cathode material comprises foamed nickel, graphene layers and silicon layers, wherein the graphene layers and the silicon layers are sequentially and alternately arranged on the foamed nickel, and the graphene layer is arranged on the topmost layer; wherein the number of the silicon layers is n, n is more than or equal to 1 and less than or equal to 20, and the number of the graphene layers is n + 1; the multilayer silicon/graphene composite lithium battery negative electrode material is 3 A.g-1The charge and discharge cycle is 500 circles under current, and the cycle retention rate is over 60 percent; the preparation method of the multilayer silicon/graphene composite lithium battery cathode material comprises the following steps:
step 1, pressing foamed nickel into a wafer, and cleaning for later use;
step 2, adding graphene oxide powder into absolute ethyl alcohol, and performing ultrasonic dispersion for 30-60min to prepare a 1-5M graphene oxide solution;
step 3, cleaning the nano silicon, and then adding the nano silicon into absolute ethyl alcohol: preparing a silicon dispersion solution with the concentration of 1-5M in a mixed solution of 9:1 ethylene glycol;
step 4, soaking the foamed nickel into the graphene oxide solution, taking out the foamed nickel, and drying the foamed nickel in an inert atmosphere at the temperature of 60-90 ℃ for 10-15 min;
step 5, soaking the foamed nickel treated in the step 4 into a silicon dispersion solution, taking out and drying in an inert atmosphere at the temperature of 60-90 ℃ for 5-10 min;
step 6, repeating the steps 4 to 5 to prepare the silicon/graphene composite lithium battery cathode material with n silicon layers and n being more than or equal to 1 and less than or equal to 20;
step 7, pressing the silicon/graphene composite lithium battery cathode material prepared in the step 6 into a sheet at 8-10 Mpa by using a tablet press;
and 8, putting the slices into a vacuum tube furnace, and reducing graphene oxide in an inert atmosphere at 550-650 ℃, wherein the heat treatment process of the vacuum tube furnace is as follows: the temperature rising speed is 5 ℃/min, the temperature rises to 550-650 ℃, and the temperature is kept for 2 h; and obtaining the multilayer silicon/graphene composite lithium battery cathode material of the foamed nickel collector.
2. The preparation method of the multilayer silicon/graphene composite lithium battery anode material according to claim 1, wherein the cleaning process of the nickel foam in the step 1 is as follows: preparing a 4-6M hydrochloric acid solution, adding foamed nickel pressed into a wafer into the hydrochloric acid solution, ultrasonically cleaning for 10-20min, and then cleaning with absolute ethyl alcohol.
3. The preparation method of the multilayer silicon/graphene composite lithium battery anode material according to claim 1, wherein the cleaning process of the nano-silicon in the step 3 is as follows: dropping HF into absolute ethyl alcohol: deionized water 1: 1, preparing 4-6M HF solution; and then adding the nano silicon into an HF solution, carrying out ultrasonic cleaning for 10-20min, and then centrifuging or carrying out suction filtration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611222585.7A CN106784700B (en) | 2016-12-27 | 2016-12-27 | Multilayer silicon/graphene composite lithium battery cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611222585.7A CN106784700B (en) | 2016-12-27 | 2016-12-27 | Multilayer silicon/graphene composite lithium battery cathode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106784700A CN106784700A (en) | 2017-05-31 |
| CN106784700B true CN106784700B (en) | 2020-02-18 |
Family
ID=58924691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611222585.7A Active CN106784700B (en) | 2016-12-27 | 2016-12-27 | Multilayer silicon/graphene composite lithium battery cathode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106784700B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108666566B (en) | 2017-03-31 | 2021-08-31 | 华为技术有限公司 | Method for preparing electrode material, electrode material and battery |
| CN109244377A (en) * | 2017-07-10 | 2019-01-18 | 力信（江苏）能源科技有限责任公司 | A kind of preparation method of negative electrode of lithium ion battery Si-C composite material |
| CN108365202A (en) * | 2018-02-22 | 2018-08-03 | 中国科学技术大学 | A kind of lithium carbon composite and preparation method thereof, electrode slice and lithium metal battery |
| CN110197896A (en) * | 2018-02-26 | 2019-09-03 | 华为技术有限公司 | A kind of composite material and preparation method |
| CN109755508A (en) * | 2018-12-18 | 2019-05-14 | 湘潭大学 | A kind of preparation method of silicon/graphene MULTILAYER COMPOSITE membrane negative electrode material |
| CN110112364B (en) * | 2019-04-26 | 2021-02-19 | 珠海冠宇电池股份有限公司 | Multilayer composite negative electrode material, preparation method thereof, negative plate and lithium battery |
| CN110931723A (en) * | 2019-10-16 | 2020-03-27 | 江苏镭明新材料科技有限公司 | Preparation method of 0D/2D nano-layered structure Si-RGO composite material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103854881B (en) * | 2012-11-30 | 2016-12-21 | 海洋王照明科技股份有限公司 | A kind of preparation method of graphene/carbon nano-tube combination electrode |
| CN103538312B (en) * | 2013-09-10 | 2016-05-18 | 浙江工业大学 | A kind of alternately stratiform graphene oxide/polyvinyl alcohol dielectric material and preparation method thereof |
| CN103928658B (en) * | 2013-12-30 | 2016-06-29 | 福建省诺希新材料科技有限公司 | The preparation method of a kind of graphene/silicon composite anode materials and goods |
| CN104269515B (en) * | 2014-09-19 | 2016-08-17 | 清华大学深圳研究生院 | A kind of anode plate for lithium ionic cell and preparation method thereof, lithium ion battery |
| KR101777714B1 (en) * | 2015-06-09 | 2017-09-12 | 성균관대학교산학협력단 | Graphene-silicon composite and preparing method of the same |
| CN106241776A (en) * | 2016-07-13 | 2016-12-21 | 南京邮电大学 | A kind of preparation method of the graphene composite thin film of LBL self-assembly |
-
2016
- 2016-12-27 CN CN201611222585.7A patent/CN106784700B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106784700A (en) | 2017-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106784700B (en) | Multilayer silicon/graphene composite lithium battery cathode material and preparation method thereof | |
| Liang et al. | High-energy flexible quasi-solid-state lithium-ion capacitors enabled by a freestanding rGO-encapsulated Fe 3 O 4 nanocube anode and a holey rGO film cathode | |
| CN106505200B (en) | carbon nanotube/graphene/silicon composite lithium battery cathode material and preparation method thereof | |
| CN111384387A (en) | Lithium ion battery and preparation method thereof | |
| CN109950476A (en) | A kind of lithium anode material and its preparation method and application | |
| CN102394305A (en) | Foamy copper oxide/copper lithium ion battery anode and preparation method thereof | |
| CN105609761B (en) | A kind of application of CuCl/Cu composite materials | |
| CN106784752A (en) | Lithium ion battery loose structure Si/Cu combination electrodes and its manufacture method | |
| CN104966814A (en) | High-security metallic lithium cathode and preparation method thereof | |
| CN108346793A (en) | A kind of nano-silicon preparation method and application with porous structure | |
| CN106876684A (en) | A kind of lithium battery silicium cathode material, negative plate and the lithium battery prepared with it | |
| CN111370656B (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN104638248A (en) | Method for preparing graphene/lead compound composite material | |
| Kim et al. | Nanoporous silicon flakes as anode active material for lithium-ion batteries | |
| CN109244531A (en) | A kind of high purity copper matrix graphite alkene composite lithium ion cell and preparation method thereof | |
| CN104600259A (en) | Lithium battery negative electrode material with lamellar structure and preparation method of lithium battery negative electrode material | |
| CN107026266B (en) | A kind of lithium ion battery CNTs/Fe2O3The preparation method of/C composite negative pole material | |
| CN115566170A (en) | Preparation method of high-energy-density quick-charging lithium ion battery cathode material | |
| CN114613613B (en) | Polydopamine/graphene composite material lithium ion hybrid capacitor and preparation method thereof | |
| CN115275166A (en) | Long-life graphite composite material and preparation method thereof | |
| CN112290025B (en) | Preparation method of electrode material based on carbonized kelp and lithium-sulfur battery | |
| CN115207304A (en) | Graphite cathode composite material, preparation method thereof and lithium ion battery | |
| Nam et al. | Effect of Flame-Retarding Additives on Surface Chemistry of Electrodes in Li-Ion Batteries | |
| CN109935821B (en) | SiO (silicon dioxide)xPreparation method of-G/PAA-PANI/graphene composite material | |
| CN109411723B (en) | Preparation method of graphene/graphite lithium ion battery negative electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |