CN115763823A - Preparation method and application of laser-induced manganese oxide/graphene array - Google Patents
Preparation method and application of laser-induced manganese oxide/graphene array Download PDFInfo
- Publication number
- CN115763823A CN115763823A CN202211401977.5A CN202211401977A CN115763823A CN 115763823 A CN115763823 A CN 115763823A CN 202211401977 A CN202211401977 A CN 202211401977A CN 115763823 A CN115763823 A CN 115763823A
- Authority
- CN
- China
- Prior art keywords
- laser
- lig
- array
- mno
- induced
- 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
Images
Classifications
-
- 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 the technical field of graphene materials, in particular to preparation of a laser-induced manganese oxide/graphene arrayA method and an application thereof. The preparation method comprises the steps of firstly pasting the PI film on the copper foil, then carrying out laser scribing on the PI film to induce a PI column-LIG array, adding a manganese source on the array, and carrying out laser thermal processing on the manganese source to MnO x The nano particles are simultaneously anchored to the LIG array, and part of PI laser of a plurality of PI columns is induced into LIG, wherein the LIG is composed of copper foil, PI columns and MnO anchored x And (3) forming a laser-induced manganese oxide/graphene array by the LIG array of the nanoparticles. Preparation of MnO in accordance with the present invention x The method of the @ LIG array is simple and convenient, and can generate and anchor manganese oxide nanoparticles in situ and realize the regulation and control of the array structure; mnO (MnO) x The @ LIG array can be used as a host material of a lithium metal battery cathode, and the prepared lithium metal battery has the advantages of low nucleation overpotential, good cycle stability, excellent rate capability and the like.
Description
Technical Field
The invention relates to the technical field of graphene materials, in particular to a preparation method and application of a laser-induced manganese oxide/graphene array.
Background
With the continuous development of new energy, the traditional lithium ion battery (theoretical energy density is about 387 Wh/kg) based on graphite and intercalation compound can not meet the urgent requirements of new energy electric vehicles, large-scale energy storage systems and the like on high energy density energy storage technology, so a new generation of high specific energy storage system needs to be developed. Metallic lithium as the lightest metal (0.534 g/cm) 3 ) The material has extremely high theoretical specific capacity (3860 mAh/g) and the lowest reduction potential (-3.04V vs. standard hydrogen electrode), and is the best choice for the future high-capacity secondary battery cathode material. In recent years, the lithium metal negative electrode has been a hot research point in the battery field by virtue of its theoretical energy advantages, but its safety and commercialization process still face huge challenges, and the main problems are: (1) The lithium metal cathode has uncontrollable dendritic crystal growth characteristics, so that a diaphragm is easy to pierce to cause short circuit of a battery, and serious fire hazard and even explosion hidden danger are brought; (2) The high reactivity of metallic lithium causes a large number of side reactions at the electrode/electrolyte interface, the decomposed electrolyte product forms an electronic insulating Solid Electrolyte Interface (SEI) on the surface of deposited lithium, a large amount of 'dead lithium' is generated and the electrolyte is continuously consumed, resulting in low charge-discharge efficiency of the electrode and rapid capacity fading; (3) The disordered deposition and dissolution process of lithium is accompanied by a great change in the volume of the electrode, causing the internal structure of the battery to be destroyed and fail. Thus, the dendrite problem of the metallic lithium is solved and obtainedThe lithium metal battery with stable cycle performance and high safety performance has important scientific significance and practical application value.
In recent years, porous carbon materials (such as carbon nanotubes, carbon nanofibers, carbon nanospheres and the like) with larger specific surface area and rich pore channel structures are widely applied to modification of the negative electrode of a lithium metal battery, and meanwhile, the lithium affinity can be improved by adding a transition metal base material, the nucleation overpotential of metal lithium is reduced, and the deposition behavior of lithium ions is improved. The graphene material is widely applied to various energy storage materials by virtue of the characteristics of high conductivity and excellent mechanical and thermal properties, and can be effectively functionalized by compounding with different oxides. However, most of the existing processes for preparing metal oxide/graphene composite materials require harsh conditions such as high temperature, high pressure, inert gas atmosphere and the like, and the preparation process is complex, and finally, a binder is added to coat a current collector to be used as a host material of a negative electrode of a lithium metal battery. Therefore, it is required to develop a simple and efficient preparation method of the metal oxide/graphene composite material and apply the metal oxide/graphene composite material to a negative electrode of a lithium metal battery.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a laser-induced manganese oxide/graphene array, wherein the graphene modified by manganese oxide nanoparticles is generated through two times of laser induction, and the synthesis step of the composite material array is simple and convenient; combining the composite material with copper foil and PI column to obtain MnO x @ LIG array, mnO x The @ LIG array can be used as a host material of a lithium metal battery cathode, and the prepared lithium metal battery has the advantages of low nucleation overpotential, good cycle stability, excellent rate capability and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a laser-induced manganese oxide/graphene array, which comprises the following steps:
s1, attaching a copper foil current collector to a substrate, and then attaching a Polyimide (PI) film to a copper foil;
s2, performing laser scribing with the machining depth of 100% on the PI film, enabling the PI film at the scribed part to be induced into a graphene (LIG) array through laser, and scribing and dividing the PI film which is not machined into a plurality of PI columns;
s3, adding a manganese source to the PI columns and the LIG array to prepare a precursor, then carrying out laser processing on all areas of the surface of the precursor, and carrying out thermal processing on the manganese source to MnO by using laser x Nanoparticles simultaneously anchored to the LIG array and upper PI laser induced LIG of multiple PI columns with MnO simultaneously anchored x The nano particles are put in LIG to obtain a composite material consisting of copper foil, PI column and anchored MnO x A laser-induced manganese oxide/graphene array consisting of LIG arrays of nanoparticles.
Preferably, the laser scribing is CO 2 And laser engraving, wherein the size of a light spot of the laser scribing is 0.2mm.
Preferably, in step S2, the laser scribing is performed by scribing line by line and column by column, and the line pitch and the column pitch of the scribing lines are equal.
Preferably, in step S2, the laser scribing process parameters are as follows: the processing area is (30-60) mmX (30-60) mm, the line width of the scribing line is 0.2-0.3 mm, the spacing of the scribing line is 0.3-0.6 mm, and the top area of the PI column is (0.3-0.6) mmX (0.3-0.6) mm.
Preferably, in step S3, the manganese source is a manganese (ii) acetylacetonate solution, the solvent of the manganese (ii) acetylacetonate solution is N, N-dimethylformamide, and the concentration of the manganese (ii) acetylacetonate solution is 0.04-0.06 g/mL.
Preferably, in step S3, the manganese source is present at 22 to 25pmol/mm 2 The amount of (d) was added to the PI column and LIG array.
Preferably, in step S3, the processing depth of the laser processing is 20 to 50%.
The invention also provides application of the laser-induced manganese oxide/graphene array in preparation of a lithium metal battery cathode.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a laser-induced manganese oxide/graphene array, which is characterized in that graphene modified by manganese oxide nanoparticles is generated through two laser-induced reactions, the synthesis steps of the composite material are simple and efficient, the manganese oxide nanoparticles are generated in situ by utilizing laser heat, and the manganese oxide nanoparticles are anchored in an LIG array to realize the regulation and control of metal ions.
The composite material is combined with a copper foil and a PI column to prepare MnO x The @ LIG array has novel hierarchical structure of material, good overall stability and MnO x The @ LIG array can be used as a host material of a lithium metal battery cathode, wherein a good current path is formed between the LIG and the copper foil, the flexible PI column not only serves as a binder, but also can effectively buffer the huge volume expansion of metal lithium in the charge-discharge process, and the three-dimensional porous structure of the LIG and MnO x The lithium affinity of the nano particles can effectively reduce the nucleation overpotential of the metal lithium, improve the deposition behavior of the lithium metal to induce the uniform deposition and dendrite-free growth of the metal lithium, so that the prepared lithium metal battery has the advantages of low nucleation overpotential, good cycle stability, excellent rate capability and the like.
Drawings
FIG. 1 is MnO x A schematic vertical cross-sectional structure of a @ LIG array;
FIG. 2 shows MnO x An optical picture of the @ LIG array;
FIG. 3 shows MnO x Scanning electron microscopy images of the @ LIG array;
FIG. 4 shows a graph formed with MnO x A nucleation overpotential map of a lithium metal battery with a @ LIG array as a negative electrode material;
FIG. 5 shows a MnO x A cycle performance diagram of a lithium metal battery with the @ LIG array as a negative electrode material;
FIG. 6 shows a graph formed with MnO x Rate performance plot of lithium metal battery with @ LIG array as negative electrode material.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1 preparation of laser-induced manganese oxide/graphene arrays
Commercial CO used in this example 2 The laser engraving machine is a 3020 type laser engraving machine and is purchased from Shanghai Pioneer and commerce GmbH.
1. Flatly covering a 7cm × 7cm copper foil current collector with the thickness of 0.015mm on a 15cm × 15cm acrylic plate, and then attaching a 10cm × 10cm commercial Polyimide (PI) adhesive tape with the thickness of 0.06mm on the copper foil and washing with absolute ethyl alcohol;
2. under air atmosphere, with commercial CO 2 Carrying out first laser processing on the PI adhesive tape in the step 1 by a laser engraving machine, wherein the processing area is a square with the size of 41.6mm multiplied by 41.6mm, and the used laser parameters are as follows: the size of a light spot is 0.2mm, the scanning speed is 50mm/s, and the processing depth is 0.06mm (the processing depth is 100%); the PI film was scribed line by line in a processing region so that the PI in the scribed portion was induced to be LIG, each line had a width of 0.2mm and a spacing distance of 0.4mm, the scribed portion after laser processing was a 69 row x 69 column laser-induced graphene (LIG) array, and the remaining unprocessed PI film in the processing region was scribed and divided into a plurality of 0.4mm x 0.4mm PI pillars.
3. Uniformly dropwise adding 0.2mL of 0.05g/mL manganese (II) acetylacetonate organic solution on the LIG array and the PI column prepared in the step 2, wherein the used solvent is N, N-Dimethylformamide (DMF), and drying for 5min in a constant-temperature forced air drying oven at 80 ℃ to obtain a precursor;
4. with commercial CO 2 And (3) carrying out line-by-line laser scanning on the precursor in the step (3) without intervals by using a laser engraving machine, wherein the processing area covers the surface of the whole precursor, and the used laser parameters are as follows: the size of a light spot is 0.2mm, the scanning speed is 100mm/s, and the processing depth is 0.015mm (the processing depth is 25%); manganese acetylacetonate is lased after laser processingHot working to MnO x Nanoparticles anchored to the LIG array, the laser machined part of the PI columns (0.015 mm) induced to LIG, also anchored with MnO x Nanoparticles, vertical cross-sectional structure after laser processing as shown in FIG. 1, with MnO anchored at the scribed part (line width 0.2 mm) x LIG array of nanoparticles, and PI pillars (thickness 0.045mm, lower part) scribed into multiple 0.4mm wide and anchored with MnO x LIG (thickness 0.015mm, upper part) of nanoparticles, finally obtained consisting of copper foil, PI columns and anchored MnO x LIG arrays of nanoparticles constituting laser-induced manganese oxide/graphene arrays, i.e. MnO x The @ LIG array.
For MnO x The @ LIG array was used for morphology characterization, and MnO was shown in FIGS. 2 and 3, respectively x The optical diagram and the scanning electron microscope diagram of the @ LIG array show that the obvious array structure of 69 rows by 69 columns is observed, wherein the scribed part is anchored with MnO x LIG array of nanoparticles, the remainder being a plurality of 0.4mm by 0.4mm square shaped PI pillars divided by scribe lines and also anchored with MnO x LIG of nanoparticles.
Example 1 with MnO x Performance characterization of lithium metal battery with @ LIG array as negative electrode material
The MnO is added x The @ LIG array is cut into circular pole pieces with the diameter of 12mm, and the circular pole pieces are used as a lithium metal battery negative electrode host material to carry out electrochemical performance test.
1. Characterization of nucleation overpotentials
Assembling the half cell: mnO of 12mm in diameter x The @ LIG array circular pole piece and the metal lithium foil with the same size are assembled into Li | MnO in a glove box which is filled with argon and has the water oxygen content lower than 0.1ppm x @ LIG half cell. The electrolyte system selected to contain 2wt% of lithium nitrate (LiNO) 3 ) Electrolyte additive and 1 mol/L1, 3-Dioxolane (DOL)/glyme (DME) (v/v = 1) solution of lithium bistrifluoromethanesulfonimide (LiTFSI), and the separator was a commercial polypropylene porous membrane.
Electrochemical testing: li | | | MnO x @ LIG half cell is firstly 0.05mA/cm 2 Is cycled between 0.01 and 3VLoop 5 times, then at 1mA/cm 2 Repeatedly depositing/stripping at a current of 1mAh/cm 2 The nucleation overpotential of the metal lithium is shown in fig. 4, the size of the nucleation overpotential is the difference value between the lowest voltage value and the stable voltage value during lithium deposition, and Li | | MnO x The nucleation overpotential of the @ LIG half cell was only 4.5mV, indicating the three-dimensional porous structure of LIG and MnO x The lithium-philic characteristic of the nano-particles can effectively reduce the nucleation overpotential of the metallic lithium.
2. Characterization of cycling Performance
Assembling the symmetrical battery: for Li | MnO first x The @ LIG half cell is subjected to electrodeposition with a discharge current of 0.5mA/cm 2 Pre-depositing 20mAh/cm 2 The metallic lithium of (4); then the half-cell was disassembled in a glove box, and the lithium composite metal negative electrode Li @ MnO was taken out x @ LIG, washing residual electrolyte on surface with excessive DME, and taking two pieces of composite lithium negative electrode Li @ MnO containing same metal lithium capacity x @ LIG assembled into Li @ MnO x @LIG||Li@MnO x The @ LIG symmetrical battery and the electrolyte system are characterized as above.
Electrochemical testing: li @ MnO x @LIG||Li@MnO x @ LIG symmetrical battery at 10mA/cm 2 Repeatedly depositing/stripping at 10mAh/cm under the current 2 The cycling performance of the lithium metal of (2) is shown in fig. 5, and the symmetric cell shows a stable cycling profile within 2000 hours (at least 1000 cycles).
3. Characterization of rate Performance
Assembling the full cell: for Li | MnO first x The @ LIG half cell is subjected to electrodeposition with discharge current of 0.5mA/cm 2 Pre-deposition of 10mAh/cm 2 The metallic lithium of (4); then the half-cell is disassembled in a glove box, and the composite metal lithium cathode Li @ MnO is taken out x @ LIG, and washing residual electrolyte on the surface with excess DME; the active matter loading is 4.5mg/cm 2 The lithium iron phosphate (LFP) positive pole piece and the composite metal lithium negative pole are placed in a glove box to be assembled into Li @ MnO x @ LIG | | LFP full cell. The system using the electrolyte was 1mol/L lithium hexafluorophosphate (LiPF) 6 ) Ethylene Carbonate (EC)/diethyl carbonate (DEC) (v/v = 1) solution, and a polypropylene porous membrane as a separator material。
Electrochemical testing: li @ MnO x The whole cell of @ LIG | | | LFP is subjected to charge-discharge test at a multiplying power of 0.1-5C and between 2.4 and 4V, the multiplying power performance is shown in figure 6, and Li @ MnO x The reversible capacities of the @ LIG | | | LFP full battery at 1C, 2C and 5C are respectively as high as 140 mAh/g, 130 mAh/g and 100mAh/g, which indicates that the PI column can effectively buffer huge volume expansion of metal lithium in the charging and discharging processes, so that the full battery has excellent rate capability.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (8)
1. The preparation method of the laser-induced manganese oxide/graphene array is characterized by comprising the following steps:
s1, attaching a copper foil current collector to a substrate, and then attaching a Polyimide (PI) film to the copper foil;
s2, performing laser scribing with the processing depth of 100% on the PI film, enabling the PI film at the scribing part to be induced into a graphene (LIG) array through laser, and scribing and dividing the residual unprocessed PI film into a plurality of PI columns;
s3, adding a manganese source to the PI columns and the LIG array to prepare a precursor, then carrying out laser processing on all areas of the surface of the precursor, and carrying out thermal processing on the manganese source to MnO by using laser x Nanoparticles anchored to the LIG array and MnO anchored to the LIG while upper PI laser-inducing portions of the PI pillars into the LIG x The nano particles are put in LIG to obtain a composite material consisting of copper foil, PI column and anchored MnO x A laser-induced manganese oxide/graphene array consisting of LIG arrays of nanoparticles.
2. The method for preparing a laser-induced manganese oxide/graphene array according to claim 1, wherein the laser scribing is CO 2 And laser engraving, wherein the spot size of the laser scribing is 0.2mm.
3. The method for preparing a laser-induced manganese oxide/graphene array according to claim 1, wherein in step S2, the laser scribing is performed line by line and column by column, and the line spacing and the column spacing of the scribing are equal.
4. The method for preparing a laser-induced manganese oxide/graphene array according to claim 1, wherein in step S2, the laser scribing process parameters are as follows: the processing area is (30-60) mmX (30-60) mm, the line width of the scribing line is 0.2-0.3 mm, the spacing of the scribing line is 0.3-0.6 mm, and the top area of the PI column is (0.3-0.6) mmX (0.3-0.6) mm.
5. The method according to claim 1, wherein in step S3, the manganese source is a manganese (ii) acetylacetonate solution, a solvent of the manganese (ii) acetylacetonate solution is N, N-dimethylformamide, and a concentration of the manganese (ii) acetylacetonate solution is 0.04-0.06 g/mL.
6. The method of claim 1, wherein in step S3, the manganese source is 22-25 pmol/mm 2 The amount of (d) was added to the PI column and LIG array.
7. The method for preparing a laser-induced manganese oxide/graphene array according to claim 1, wherein in the step S3, the processing depth of the laser processing is 20-50%.
8. The laser-induced manganese oxide/graphene array prepared by the preparation method of any one of claims 1 to 7 is applied to the preparation of a lithium metal battery cathode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211401977.5A CN115763823B (en) | 2022-11-10 | 2022-11-10 | Preparation method and application of laser-induced manganese oxide/graphene array |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211401977.5A CN115763823B (en) | 2022-11-10 | 2022-11-10 | Preparation method and application of laser-induced manganese oxide/graphene array |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115763823A true CN115763823A (en) | 2023-03-07 |
| CN115763823B CN115763823B (en) | 2023-08-04 |
Family
ID=85368851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211401977.5A Active CN115763823B (en) | 2022-11-10 | 2022-11-10 | Preparation method and application of laser-induced manganese oxide/graphene array |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115763823B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116230869A (en) * | 2023-05-06 | 2023-06-06 | 宁德时代新能源科技股份有限公司 | Negative electrode plate, preparation method, battery cell, battery and power utilization device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107658453A (en) * | 2017-09-20 | 2018-02-02 | 中南大学 | Negative electrode of lithium ion battery manganese monoxide/graphene composite material and preparation method thereof |
| CN109686593A (en) * | 2019-01-17 | 2019-04-26 | 西安交通大学 | One kind is based on secondary laser irradiation preparation MnO2The method of/graphene combination electrode |
| CN110620238A (en) * | 2019-09-24 | 2019-12-27 | 深圳先进技术研究院 | Current collector and preparation method thereof, negative electrode and secondary battery |
| CN112466678A (en) * | 2020-10-27 | 2021-03-09 | 西安电子科技大学 | Laser induced MnO2Graphene micro supercapacitor and manufacturing method thereof |
-
2022
- 2022-11-10 CN CN202211401977.5A patent/CN115763823B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107658453A (en) * | 2017-09-20 | 2018-02-02 | 中南大学 | Negative electrode of lithium ion battery manganese monoxide/graphene composite material and preparation method thereof |
| CN109686593A (en) * | 2019-01-17 | 2019-04-26 | 西安交通大学 | One kind is based on secondary laser irradiation preparation MnO2The method of/graphene combination electrode |
| CN110620238A (en) * | 2019-09-24 | 2019-12-27 | 深圳先进技术研究院 | Current collector and preparation method thereof, negative electrode and secondary battery |
| CN112466678A (en) * | 2020-10-27 | 2021-03-09 | 西安电子科技大学 | Laser induced MnO2Graphene micro supercapacitor and manufacturing method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116230869A (en) * | 2023-05-06 | 2023-06-06 | 宁德时代新能源科技股份有限公司 | Negative electrode plate, preparation method, battery cell, battery and power utilization device |
| CN116230869B (en) * | 2023-05-06 | 2023-09-29 | 宁德时代新能源科技股份有限公司 | Negative electrode plate, preparation method, battery cell, battery and power utilization device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115763823B (en) | 2023-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102394305B (en) | Foamy copper oxide/copper lithium ion battery anode and preparation method thereof | |
| CN101572305B (en) | Preparation method of LiFePO*/C cathode material with high rate performance | |
| CN113629236B (en) | Composite metal lithium cathode and preparation method and application thereof | |
| CN111554883B (en) | Pre-lithiation method for preparing electrode membrane based on dry method | |
| CN103682251B (en) | A kind of porous iron sesquioxide/carbon nanosheet composite and preparation method thereof and its application in preparing lithium ion battery | |
| CN114220947B (en) | Lithium metal battery negative electrode, current collector, preparation method of current collector and battery | |
| CN110010895A (en) | Carbon fiber loaded magnesium oxide particle crosslinking nano chip arrays composite material and preparation method and application | |
| CN111987278A (en) | Composite diaphragm for lithium metal secondary battery and preparation method and application thereof | |
| CN110676433B (en) | Composite lithium cathode, preparation method thereof and lithium battery | |
| CN113506914A (en) | Ternary lithium ion battery electrolyte and lithium ion battery containing same | |
| CN112803026A (en) | Lithium negative electrode for dendrite-free all-solid-state battery and preparation method and application thereof | |
| CN115763823B (en) | Preparation method and application of laser-induced manganese oxide/graphene array | |
| CN115133023A (en) | Preparation method of doped modified ferric sodium pyrophosphate cathode material | |
| CN113644264B (en) | Modification method of natural graphite negative electrode material | |
| CN112786885B (en) | Long-life and dendrite-free metal lithium negative electrode for lithium battery and preparation method and application thereof | |
| CN113636974A (en) | Compound for reducing lithium dendrite, preparation method thereof, modification liquid, solid electrolyte membrane, preparation method thereof and lithium metal secondary battery | |
| CN110707286A (en) | High-energy-density lithium ion battery integrated electrode and preparation method thereof | |
| CN114843491A (en) | High-capacity and high-cycle-stability cathode material and preparation method thereof | |
| CN114665082A (en) | Negative electrode material and preparation method and application thereof | |
| CN112216809B (en) | Metal cathode, preparation method thereof and lithium ion battery | |
| CN112531165A (en) | Alkali metal cathode composite protective film and preparation method thereof, alkali metal cathode and alkali metal secondary battery | |
| CN113363422B (en) | Preparation method of low-negative-electrode-expansion long-cycle lithium ion battery and lithium ion battery | |
| CN113659135B (en) | Application of iron sulfide in lithium iron phosphate secondary battery | |
| CN116826050A (en) | Tin/graphene anode material, preparation method thereof and sodium metal battery | |
| CN116826059B (en) | Lithium battery negative electrode material applied to marine environment and preparation method thereof |
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 |