CN111477837A - Foam metal sulfide anode for thermal battery and preparation method thereof - Google Patents
Foam metal sulfide anode for thermal battery and preparation method thereof Download PDFInfo
- Publication number
- CN111477837A CN111477837A CN202010333286.0A CN202010333286A CN111477837A CN 111477837 A CN111477837 A CN 111477837A CN 202010333286 A CN202010333286 A CN 202010333286A CN 111477837 A CN111477837 A CN 111477837A
- Authority
- CN
- China
- Prior art keywords
- foam
- metal sulfide
- thermal battery
- anode
- foam metal
- 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.)
- Pending
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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/06—Electrodes for primary cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/36—Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of thermal battery anode materials, and particularly relates to a foam metal sulfide anode for a thermal battery and a preparation method thereof. The prepared thin electrode can be used for a high-power output type thermal battery, the use of an anode substrate is reduced, the monomer height is reduced, and the weight ratio power and the volume ratio power of the thermal battery are further improved.
Description
Technical Field
The invention belongs to the technical field of thermal battery anode materials, and particularly relates to a foam metal sulfide anode for a thermal battery and a preparation method thereof.
Background
Thermal batteries have been widely used in various weaponry because of their short activation time, long storage life, high output power, strong mechanical temperature and environmental adaptability, and the like. With the continuous development and the updating of military weaponry, the requirement on the performance of a thermal battery is higher and higher, the requirement on the working time of the thermal battery is longer and longer, the requirement on the output power is higher and higher, and then the thermal battery is required to have the characteristics of higher specific power, higher specific energy and the like. The research shows that the ideal anode material of the thermal battery needs to have the following advantages: 1) the electromotive force is more than 3V; 2) the thermal stability is more than 800 ℃; 3) the conductivity is high, and large current discharge can be realized; 4) good dynamic properties (high rate capacity); 5) good compatibility with molten salts (no or as little fusion to molten salts as possible); 6) low molecular weight (high coulomb/mole ratio, i.e., high electrochemical capacity); 7) non-embedded (multi-phase) discharge; 8) the reaction product is not fused in molten salt, and has high conductivity (preventing the internal resistance from increasing in the discharging process) and thermal stability; 9) high thermal conductivity, facilitating rapid activation; 10) the heat capacity is low, minimizing the heat input required from the heating fins; 11) stably existing in the storage temperature range (-50 ℃ to 70 ℃), and is not easy to react with water, oxygen and CO2And the like; 12) the material is simple to prepare, reasonable in cost, wide in source and environment-friendly (green).
Today, the main reason for limiting the output performance of thermal batteries is the material and preparation method of the positive electrode of the thermal battery.
In the aspect of positive electrode materials, metal sulfides are widely used as positive electrode materials in thermal batteries, such as FeS, due to their advantages of extremely high theoretical capacity, low solubility in molten salts, and the like2、CoS2、NiS2But still have some drawbacks, such as FeS2Initial dischargeVoltage spike and low conductivity in the period, which not only prolongs the activation time, but also causes the discharge voltage and specific capacity to be obviously reduced, and more importantly, Fe S2When thermally decomposed at high temperature, sulfur vapor is generated, and the sulfur vapor reacts with L i or with a lithium compound in an electrolyte to generate a solid insulating layer L i2S, which prevents the transmission of electrons and ions, not only reduces the amount of active material of the negative electrode and destroys the electrolyte structure, but also generates a large amount of heat to sharply increase the internal temperature of the thermal battery, resulting in FeS2Further decomposition occurs, and when the sulfur vapor is excessive, the sulfur vapor reacts with an iron protective layer inside the thermal battery, so that the battery structure is damaged; CoS2To H2O and O2Is very sensitive, and is very easy to decompose in humid air, and the decomposition product CoSO4The resistance is extremely high, the polarization internal resistance of the electrode of the thermal battery can be seriously increased, the discharge capacity of the thermal battery can be seriously reduced, and the reliability of the thermal battery can be influenced; NiS2The phase is impure during the preparation process and the voltage decays too fast during the discharge process. Therefore, metal sulfides are often combined with other materials, such as graphene/cobalt sulfide composite electrode materials disclosed in patent publication No. CN 111005036A.
In terms of preparation methods, research on novel high-potential high-specific-energy positive electrode materials and preparation methods of thinned positive electrodes is being developed at home and abroad. For a thermal battery with high power output, the thinning anode not only can increase the specific power of the thermal battery, but also can effectively improve the safety of the thermal battery. At home and abroad, thin anodes are researched and prepared mainly by a delayed flow method and an ion spraying method, wherein the ion spraying method is to use an anode active substance (such as FeS)2) The thin positive plate is obtained by directly spraying the solution on an electrode, but the ion spraying equipment is very expensive, so that the ion spraying equipment cannot be applied in a large scale; the flow extension method is to mix the positive active material and the binder into a suspension liquid and then attach the suspension liquid on the electrode, the process is complex, the used electrode is metal foam, graphite paper and the like, the metal foam can effectively improve the mechanical property of the positive plate due to high porosity, but the metal foam has lower consistency with the microstructure of the positive active material, so that the increase of the mechanical property of the positive plate is realizedContact resistance with the positive electrode active material; moreover, since the metal foam does not belong to the positive active material, it reduces the content of the active material in the positive material, and thus reduces the discharge capacity thereof, for example, patent publication No. CN106058147A discloses a thermal battery CoS prepared by screen printing2A method of forming a positive electrode film.
Based on the double consideration of materials and manufacturing technology, it is important to research a positive electrode material having the advantages of both foamed metal and metal sulfide, but in the prior art, metal sulfide and foamed metal are compounded, for example, patent publication No. CN108615620A discloses a carbon nanotube/metal sulfide composite electrode using foamed nickel as a substrate and a preparation method thereof. Dissolving a carboxylated carbon nanotube and nickel nitrate hexahydrate in isopropanol, performing ultrasonic dispersion to obtain an electrodeposition solution, and performing electrodeposition in the electrodeposition solution by taking foamed nickel subjected to hydrothermal acidification as a cathode and a platinum sheet as an anode to obtain a carbon nanotube composite electrode material; and then placing the carbon nano tube/metal sulfide composite electrode in a sodium sulfide solution, and carrying out hydrothermal treatment for 6-10 h at the temperature of 70-125 ℃ to obtain the carbon nano tube/metal sulfide composite electrode with the foamed nickel as the substrate. Patent publication No. CN106067383A discloses a pseudocapacitor anode based on a cobalt nickel sulfide core-shell three-dimensional multistage nanostructure and a preparation method thereof, the anode comprises a foam nickel substrate 1, cobalt nickel sulfide nanosheets 2 located on the foam nickel substrate 1 in an array distribution mode, and cobalt nickel sulfide blades 3 connected to two sides of the cobalt nickel sulfide nanosheets 2 in a growth array distribution mode, the cobalt nickel sulfide nanosheets 2 are perpendicular to the foam nickel substrate 1, and the cobalt nickel sulfide blades 3 and the cobalt nickel sulfide nanosheets 2 are in an angle of 0-90 degrees along the opposite direction of the foam nickel substrate 1. Therefore, the prior art cannot fully solve the problems that the discharge capacity is not ideal due to the introduction of non-positive active substances and the output performance requirement of the thermal battery cannot be met by the conventional positive electrode material.
Disclosure of Invention
The invention provides a new thought and method for thinning the positive electrode of the thermal battery, can reduce the contact resistance between a matrix framework and a positive active material, has better mechanical performance, and can effectively improve the specific capacity of the thermal battery.
The specific technical scheme is as follows:
a foam metal sulfide anode for a thermal battery is composed of foam metal sulfide and metal sulfide powder.
The foam metal sulfide plays a role of a framework, so that the molding and mechanical properties of the anode are ensured, and the metal sulfide powder is used as a main active substance of the anode and is embedded into the framework, so that a binder in the anode of a traditional thermal battery is removed. Meanwhile, the chemical components of the foam metal sulfide are consistent with those of the metal sulfide, so that the contact resistance between the matrix skeleton and the positive active material is reduced.
A preparation method of a foam metal sulfide anode for a thermal battery comprises the steps of placing metal sulfide powder in an organic solvent to prepare a suspension, adding foam metal sulfide, uniformly mixing, and drying in vacuum to obtain the foam metal sulfide anode.
The metal sulfide is FeS2、CoS2、NiS2Any one of them.
The particle size of the metal sulfide powder is less than or equal to 20 mu m.
According to the invention, the particle size of the metal sulfide powder is strictly controlled, so that the metal sulfide can be fully and effectively embedded into the foam framework, the mechanical property of the positive electrode is favorably improved, and the particle size of the metal sulfide powder is also favorably controlled to be in favor of the specific surface area of the positive electrode.
The organic solvent is acetone.
The mass ratio of the metal sulfide powder to the organic solvent is x: (100-x), wherein x is 2-10.
The vacuum drying process comprises the following process conditions: the temperature is 70-100 ℃, the vacuum degree is less than or equal to-0.09 MPa, and the time is more than or equal to 24 hours.
The preparation method of the foam metal sulfide comprises the following steps: and carrying out a vulcanization reaction on the foam metal and elemental sulfur under the protection of inert gas.
The foam metal is any one of foam iron, foam cobalt and foam nickel.
The inert gas is any one of argon, helium and neon.
The sulfurization reaction has the reaction conditions that: the temperature is 500 ℃ and 600 ℃, and the time is 3-6 h.
The molar ratio of the elemental sulfur to the foam metal is more than or equal to 2: 1.
The thermal battery system applicable to the invention comprises a thermal battery system with L iB, L iSi, L iAl or L AN alloy as the negative electrode and binary L iCl-KCl, ternary L iF-L iCl-L iBr and other low-melting point electrolytes.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the foam metal sulfide is used as the framework of the anode matrix, the metal sulfide powder with the same chemical composition is used as the active substance, so that the contact resistance between the framework matrix and the active substance is effectively reduced, the internal resistance of the anode is further reduced, the metal sulfide powder can be effectively embedded into the porous framework of the foam metal sulfide, the prepared anode has good mechanical properties, and the anode material does not contain inactive substances, so that the capacity output and the utilization rate of the anode are greatly improved.
2. The preparation method has the advantages of simple preparation process, strong operability, low equipment cost and contribution to large-scale production. The prepared thin electrode can be used for a high-power output type thermal battery, the use of an anode substrate is reduced, the monomer height is reduced, and the weight ratio power and the volume ratio power of the thermal battery are further improved.
Drawings
FIG. 1: foam FeS2A matrix anode and a foam Fe matrix anode discharge performance comparison test chart;
FIG. 2: foam CoS2A comparative test chart of the discharge performance of the matrix anode and the foam Co matrix anode;
FIG. 3: foam NiS2A matrix anode and a foam Ni matrix anode discharge performance comparison test chart;
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
Foam FeS2The preparation of the positive electrode comprises the following steps:
(1) high temperature vulcanization of foamed iron
Separately putting elemental sulfur and foam iron into a high-temperature furnace according to the mol ratio of 2.05:1, introducing inert gas argon, heating to 500 ℃, heating at the speed of 2 ℃/min, and keeping the temperature for 4 hours to obtain foam FeS2；
(2)FeS2Powder ball mill
FeS with the original particle size of 98 mu m2Putting the powder into a ball mill, and grinding for 24 hours until the particle size reaches 18 mu m after grinding;
(3) preparation of suspension
Grinding the FeS2Dissolving the powder in a beaker filled with acetone solution, and fully stirring to obtain a suspension; the FeS2The mass ratio of the acetone solution to the acetone solution is 1: 49;
(4) mixing and vacuum drying
FeS prepared in the step 12Placing the foam into the suspension, and standing for 10 minutes; then putting the suspension into a vacuum drying oven, setting the drying temperature at 70 ℃ and the vacuum degree at-0.09 MPa, and drying for 24h to obtain foam FeS2And (4) a positive electrode.
Example 2
Foam CoS2The preparation of the positive electrode comprises the following steps:
1. foamed cobalt high temperature vulcanization
Separately putting elemental sulfur and foamed cobalt into a high-temperature furnace according to the mol ratio of 2.05:1, introducing inert gas argon, heating to 600 ℃, heating at the speed of 2 ℃/min, and keeping the temperature for 5 hours to obtain foamed CoS2；
2.CoS2Powder ball mill
CoS with the original particle size of 100 mu m2Putting the powder into a ball mill, and grinding for 24 hours until the particle size reaches 20 mu m after grinding;
3. preparation of suspension
Will be groundMilled CoS2Dissolving the powder in a beaker filled with acetone solution, and fully stirring to obtain a suspension; the CoS2The mass ratio of the acetone solution to the acetone solution is 1: 9, wherein x is 2-10
4. Mixing and vacuum drying
The foam obtained in the step 1 is CoS2Putting the suspension into the reactor, and standing for 10 minutes; then putting the suspension into a vacuum drying oven, setting the drying temperature at 80 ℃ and the vacuum degree at-0.09 MPa, and drying for 24h to obtain foam CoS2And (4) a positive electrode.
Example 3
Foam NiS2The preparation of the positive electrode comprises the following steps:
(1) high temperature vulcanization of nickel foam
Separately putting the elemental sulfur and the foam iron into a high-temperature furnace according to the mol ratio of 4:1, introducing inert gas argon, heating to 570 ℃, heating at the speed of 3.6 ℃/min, and keeping the temperature for 3 hours to obtain foam NiS2；
(2)NiS2Powder ball mill
Mixing NiS2Putting the powder into a ball mill, and grinding the powder until the particle size is 10 mu m;
(3) preparation of suspension
Grinding NiS2Dissolving the powder in a beaker filled with acetone solution, and fully stirring to obtain a suspension; the NiS2The mass ratio of the acetone solution to the acetone solution is 1: 19;
(4) mixing and vacuum drying
NiS prepared in the step 12Placing the foam into the suspension, and standing for 10 minutes; then putting the suspension into a vacuum drying oven, setting the drying temperature at 96 ℃, setting the vacuum degree at-0.09 MPa, and drying for 24h to obtain foam NiS2And (4) a positive electrode.
Test example 1
Comparative preparation of foam FeS2The electrical properties of the matrix positive electrode and the metallic Fe foam matrix positive electrode were obtained by directly preparing the matrix from Fe metal foam without high temperature sulfidation treatment, using L iB alloy as the negative electrode, ternary L iF-L iCl-L iBr as the electrolyte, and 400mA/cm2The current density is discharged at constant current at normal temperature, the discharge performance of the current density and the discharge performance are shown in figure 1, and the foam FeS prepared by the method can be seen from the figure2The discharge capacity and energy of the matrix anode are larger than those of a metal Fe foam matrix directly used, and the later-stage bearing capacity is stronger.
Test example 2
For comparative preparation of foam CoS2According to the method in the embodiment 2, the electrical properties of the matrix anode and the metallic Co foam matrix anode are directly prepared by taking Co metallic foam which is not subjected to high-temperature vulcanization treatment as the matrix to form the anode, taking L iB alloy as the cathode, taking ternary L iF-L iCl-L iBr as electrolyte and 200mA/cm2The current density is discharged at constant current at normal temperature, the discharge performance of the current density and the discharge performance are shown in figure 2, and the foam CoS prepared by the method can be seen from the figure2The discharge capacity and energy of the matrix anode are larger than those of a metal Co foam matrix directly used, a voltage platform is more stable, and the later-stage bearing capacity is stronger.
Test example 3
Foam NiS prepared for comparison2The electrical properties of the matrix positive electrode and the foam Ni matrix positive electrode were determined by the method of example 3, in which Ni metal foam without high temperature sulfidation was directly used as the matrix to prepare the positive electrode, L iB alloy as the negative electrode, ternary L iF-L iCl-L iBr as the electrolyte, and 100mA/cm2Constant current sum 1.0A/cm2The pulse discharges at normal temperature, the discharge performance of the pulse and the pulse is shown in figure 3, and the figure shows that the foam NiS prepared by the method of the invention2The discharge capacity and energy of the matrix anode are larger than those of the matrix directly made of metal Ni foam, the voltage platform is more stable, the pulse bearing capacity is stronger, and the internal resistance is lower.
Claims (10)
1. A foam metal sulfide anode for a thermal battery is characterized by comprising foam metal sulfide and metal sulfide powder.
2. The foam metal sulfide anode of claim 1 wherein the metal sulfide is FeS2、CoS2、NiS2Any one of them.
3. The method of claim 1, wherein the metal sulfide powder is placed in an organic solvent to prepare a suspension, the metal sulfide foam is added to the suspension and mixed uniformly, and the foam metal sulfide anode is obtained after vacuum drying.
4. The method of claim 2, wherein the metal sulfide powder has a particle size of 20 μm or less.
5. The method for preparing a foam metal sulfide positive electrode for a thermal battery according to claim 2, wherein the vacuum drying comprises the following process conditions: the temperature is 70-100 ℃, the vacuum degree is less than or equal to-0.09 MPa, and the time is more than or equal to 24 hours.
6. The method of preparing a foam metal sulfide positive electrode for a thermal battery according to claim 2, wherein the foam metal sulfide is prepared by: and carrying out a vulcanization reaction on the foam metal and elemental sulfur under the protection of inert gas.
7. The method of claim 2, wherein the metal foam is any one of iron foam, cobalt foam and nickel foam.
8. The method of claim 2, wherein the inert gas is any one of argon, helium and neon.
9. The method of claim 2, wherein the sulfidation reaction is carried out under the following conditions: the temperature is 500 ℃ and 600 ℃, and the time is 3-6 h.
10. The method for preparing a foam metal sulfide positive electrode for a thermal battery according to claim 2, wherein the molar ratio of elemental sulfur to foam metal is not less than 2: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010333286.0A CN111477837A (en) | 2020-04-24 | 2020-04-24 | Foam metal sulfide anode for thermal battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010333286.0A CN111477837A (en) | 2020-04-24 | 2020-04-24 | Foam metal sulfide anode for thermal battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111477837A true CN111477837A (en) | 2020-07-31 |
Family
ID=71764036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010333286.0A Pending CN111477837A (en) | 2020-04-24 | 2020-04-24 | Foam metal sulfide anode for thermal battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111477837A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170207488A1 (en) * | 2016-01-15 | 2017-07-20 | Aruna Zhamu | Production process for alkali metal-sulfur batteries having high volumetric and gravimetric energy densities |
| CN108701870A (en) * | 2016-01-15 | 2018-10-23 | 纳米技术仪器公司 | Alkali metal with high volume and weight energy density-sulphur battery |
| US20190006720A1 (en) * | 2017-06-28 | 2019-01-03 | Agency For Defense Development | Molten lithium-sulfur battery with solid electrolyte and method of manufacturing the same |
| CN110783540A (en) * | 2019-10-08 | 2020-02-11 | 贵州梅岭电源有限公司 | Ternary composite positive electrode material for thermal battery and preparation method thereof |
-
2020
- 2020-04-24 CN CN202010333286.0A patent/CN111477837A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170207488A1 (en) * | 2016-01-15 | 2017-07-20 | Aruna Zhamu | Production process for alkali metal-sulfur batteries having high volumetric and gravimetric energy densities |
| CN108701870A (en) * | 2016-01-15 | 2018-10-23 | 纳米技术仪器公司 | Alkali metal with high volume and weight energy density-sulphur battery |
| US20190006720A1 (en) * | 2017-06-28 | 2019-01-03 | Agency For Defense Development | Molten lithium-sulfur battery with solid electrolyte and method of manufacturing the same |
| CN110783540A (en) * | 2019-10-08 | 2020-02-11 | 贵州梅岭电源有限公司 | Ternary composite positive electrode material for thermal battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110620223B (en) | Lithium ion battery pre-lithiation silicon-carbon multilayer composite negative electrode material and preparation method thereof | |
| CN110649267B (en) | Composite metal lithium cathode, preparation method and metal lithium battery | |
| Zhang et al. | A facile synthesis of 3D flower-like NiCo2O4@ MnO2 composites as an anode material for Li-ion batteries | |
| CN101662022B (en) | Nano coating of negative electrode materials and preparation method of secondary aluminium cell using negative electrode materials | |
| CN108394884A (en) | A kind of preparation method of chitosan-based high-specific surface area nitrogen/phosphor codoping carbon nanosheet | |
| CN111969210B (en) | High-rate lithium ion battery negative electrode material and preparation method thereof | |
| CN105826527A (en) | Porous silicon-carbon composite material and preparation method and application thereof | |
| Li et al. | New electrochemical energy storage systems based on metallic lithium anode—the research status, problems and challenges of lithium-sulfur, lithium-oxygen and all solid state batteries | |
| CN111564612B (en) | High-thermal-conductivity and high-electrical-conductivity lithium battery positive electrode material and preparation method thereof | |
| CN111342014A (en) | Silicon-carbon negative electrode material of lithium ion battery and preparation method thereof | |
| CN114314673B (en) | Preparation method of flaky FeOCl nano material | |
| CN113659125A (en) | Silicon-carbon composite material and preparation method thereof | |
| WO2022151648A1 (en) | High-capacity highly stable silicon-carbon negative electrode material and preparation method therefor | |
| CN110311111B (en) | N-doped CNT in-situ coated Co nanoparticle composite material and preparation and application thereof | |
| CN114242961B (en) | Graphene/silicon oxide coated nano-silicon composite material and preparation method and application thereof | |
| CN108023085B (en) | Preparation method of carbon-coated tin dioxide nanoparticles | |
| Zhu et al. | Uniform implantation of ultrafine Cu2S nanoparticles into carbon nanowires for efficient potassium-ion battery anodes | |
| He et al. | Facile synthesis of CdCO3 cubic particles/graphene composite with enhanced electrochemical performance for lithium-ion batteries | |
| CN117497723A (en) | Preparation method of MOF-derived carbon-coated silicon nanoparticle-limited MXene composite anode material of lithium ion battery | |
| CN110649237B (en) | Iron oxide @ carbon nanocomposite and preparation method and application thereof | |
| CN115036502B (en) | Based on ZnCo2O4Method for preparing negative electrode material of sodium ion battery by hollow carbon nano ring and application thereof | |
| Liu et al. | Brush-structured sulfur–polyaniline–graphene composite as cathodes for lithium–sulfur batteries | |
| CN110061198B (en) | Silicon-carbon composite negative electrode material and preparation method and application thereof | |
| CN110212171A (en) | A kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cell | |
| CN113130879B (en) | Preparation method of high-adsorption catalytic performance cathode material of lithium-sulfur battery |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200731 |