CN113839026A - Lithium ion battery cathode composite material and preparation method thereof - Google Patents
Lithium ion battery cathode composite material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M4/5805—Phosphides
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- 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
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- 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
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium ion battery cathode composite material and a preparation method thereof, wherein the composite material is formed by superposing a plurality of spherical nanoscale red phosphorus @ carbon primary particles to form micron-sized spherical secondary particles, and the nanoscale red phosphorus @ carbon primary particles are porous carbon layers and uniformly coat the surfaces of mesoporous nano red phosphorus particles; mixing mesoporous nano red phosphorus with an organic carbon source and a carbonizing agent, and performing high-speed shearing and emulsification to prepare an emulsion; the emulsion is subjected to spray drying treatment and then placed in a closed quartz tube filled with inert gas, and the composite material is obtained through low-temperature roasting treatment.
Description
Technical Field
The invention relates to a lithium ion battery material, in particular to a lithium ion battery cathode composite material and a preparation method thereof.
Background
The rapid development of new energy automobiles and portable electronic products makes the industry put higher demands on the performance of lithium ion batteries. The positive and negative electrode materials are the key influencing the electrochemical performance of the battery, the research on the positive electrode materials has been greatly progressed in recent years, and the development of novel negative electrode materials with high specific capacity and long service life becomes the key breaking through the technical bottleneck of a new generation of lithium ion batteries. The theoretical capacity of red phosphorus can reach 2600mAh g-1And is considered to be a promising lithium ion battery cathode material. Moreover, the red phosphorus has the advantages of chemical stability, environmental friendliness, rich raw materials, mild preparation conditions and the like. However, the application of the red phosphorus negative electrode faces the problems of low electronic conductivity, severe volume expansion in the charge and discharge process, and the like. These problems cause the actual specific capacity of red phosphorus to be far lower than the theoretical value, the first coulombic efficiency to be low, the charge-discharge cycle performance to be poor and the like. Nanocrystallization and compounding with a porous carbon material are effective means for improving the electronic conductivity of red phosphorus and buffering volume expansion in the charging and discharging processes, and the industry generally adopts a mechanical ball milling method or a sublimation-condensation method to realize. However, the mechanical ball milling method has too high energy consumption and difficulty in realizing red phosphorus nanocrystallization, and although the sublimation-condensation method can realize red phosphorus nanocrystallization by combining with a carbon substrate, the process has certain potential safety hazard and is not beneficial to large-scale production. These problems severely restrict the effective use of red phosphorus anodes.
Disclosure of Invention
The invention aims to solve the technical problem of providing a lithium ion battery cathode composite material which has high specific capacity, stable structure, excellent cycle performance and rate performance and high tap density, can effectively buffer the volume expansion of red phosphorus, avoid electrode material pulverization and enhance the contact area of the red phosphorus with a conductive material and an electrolyte, and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the composite material is formed by superposing a plurality of spherical nanoscale red phosphorus and carbon primary particles to form micron-sized spherical secondary particles, wherein the nanoscale red phosphorus and carbon primary particles are uniformly coated on the surfaces of the nano red phosphorus particles by a carbon layer, the carbon layer is of a porous structure, the nano red phosphorus particles are of a mesoporous structure, and a gap microstructure is formed between the carbon layer and the nano red phosphorus particles.
The preparation method of the porous carbon-coated mesoporous red phosphorus composite material comprises the following steps:
(1) uniformly mixing commercial red phosphorus, organic amine and an alcohol additive, reacting under certain process conditions, standing, centrifuging, washing and drying to obtain mesoporous nano red phosphorus particles, wherein the mixing ratio of the commercial red phosphorus to the organic amine to the alcohol additive is 400 mg: 25mL of: 5 mL;
(2) mixing the mesoporous nano red phosphorus obtained in the step (1) with an organic carbon source and a carbonizing agent, and performing high-speed shearing and emulsification to prepare an emulsion, wherein the mass ratio of the mesoporous nano red phosphorus to the organic carbon source is 1: 0.2-5, wherein the mass ratio of the organic carbon source to the carbonizing agent is 1: 0.01-0.03;
(3) placing the emulsion obtained in the step (2) into a spray dryer, and performing spray drying treatment to obtain a precursor of the porous carbon-coated mesoporous red phosphorus material;
(4) and (4) placing the precursor obtained in the step (3) into a closed quartz tube filled with inert gas, and roasting at low temperature to obtain the porous carbon-coated mesoporous red phosphorus active composite material.
Preferably, the process conditions in the step (1) are that the reaction temperature is 150 ℃ and 250 ℃, and the time is 12-36 h.
Preferably, the organic ammonium solution in step (1) is one or more of propylenediamine, butylenediamine, hexamethylenediamine and triethanolamine.
Preferably, the alcohol additive in step (1) is one or more of ethylene glycol, propylene glycol and isopropanol.
Preferably, the organic carbon source in step (2) is one or more of sucrose, glucose, vitamin C and polypyrrole.
Preferably, the carbonizing agent in the step (2) is one or more of ferrocene, nickelocene and cobaltocene.
Preferably, the temperature of the spray drying in the step (3) is 120-220 ℃.
Preferably, the low-temperature roasting condition in the step (4) is 300-.
Compared with the prior art, the invention has the advantages that: the invention discloses a porous carbon-coated mesoporous red phosphorus composite material and a preparation method thereof, wherein micron-sized commercial red phosphorus is converted into nano red phosphorus by a liquid phase method; simultaneously, based on the action of an alcohol additive, the nano red phosphorus forms a mesoporous structure in situ; then, preparing nano red phosphorus, an organic carbon source and a carbonizing agent into emulsion by a shearing and emulsifying means, uniformly coating the carbon source and the carbonizing agent on the surface of the nano red phosphorus by utilizing a spray drying technology, and combining a plurality of nano red phosphorus @ carbon primary particles into micron-sized spherical secondary particles; and finally, carbonizing the carbon source by low-temperature roasting treatment, and forming a micropore and gap microstructure in the carbon layer to finally obtain the porous carbon-coated mesoporous nano red phosphorus composite material. The advantages are as follows:
(1) the invention takes commercial red phosphorus as a raw material, and can directly synthesize the porous carbon-coated mesoporous nano red phosphorus composite material through liquid phase reaction, shearing emulsification, spray drying and low-temperature roasting with the assistance of an alcohol additive.
(2) The prepared negative active material is a secondary spherical particle consisting of a plurality of red phosphorus/carbon nano particles, has high tap density and is beneficial to improving the energy density of the battery; meanwhile, the carbon coating layer and the nano red phosphorus in the composite material have pore structures, and gaps also exist between the carbon coating layer and the red phosphorus particles, so that the special porous structure can effectively buffer the volume expansion of the red phosphorus, avoid electrode material pulverization and enhance the contact area of the red phosphorus with a conductive material and an electrolyte. In addition, the three-dimensional conductive network constructed by the carbon coating layers among the nano particles can effectively improve the electronic conductivity of the material. These beneficial conditions are all beneficial for improving the material performance.
(3) The porous carbon-coated mesoporous red phosphorus composite material disclosed by the invention is simple and convenient in preparation process, high in yield, low in energy consumption, low in cost, easy to scale and has industrial application potential.
Drawings
FIG. 1 is a schematic structural diagram of a porous carbon-coated mesoporous nano red phosphorus composite material;
FIG. 2 is an SEM image of the mesoporous nano red phosphorus material prepared in example 1;
fig. 3 shows the specific discharge capacity, coulombic efficiency and cycle performance of the porous carbon-coated mesoporous red phosphorus composite material at 0.1C rate.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1
A porous carbon-coated mesoporous red phosphorus composite material is shown in figure 1, and is formed by superposing a plurality of spherical nanoscale red phosphorus @ carbon primary particles to form micron-sized spherical secondary particles, wherein the nanoscale red phosphorus @ carbon primary particles are carbon layers which are uniformly coated on the surfaces of the nano red phosphorus particles, the carbon layers are porous structures, the nano red phosphorus particles are mesoporous structures, and a gap microstructure is formed between the carbon layers and the nano red phosphorus particles. The preparation method comprises the following steps:
grinding 400mg of micron-sized red phosphorus for 20min, putting the ground red phosphorus into a closed reactor, adding 25mL of propylene diamine and 5mL of ethylene glycol, and carrying out ultrasonic treatment for 30 min; and (3) putting the red phosphorus particles into a thermostat to react for 24 hours at 200 ℃, cooling to normal temperature after the reaction is finished, standing, centrifuging, washing and drying to obtain the red phosphorus nanoparticles, wherein a scanning electron microscope picture of the red phosphorus nanoparticles is shown in figure 2. Mixing 300mg of nano red phosphorus particles with 240mg of cane sugar and 4.8mg of ferrocene, and carrying out high-speed shearing emulsification to prepare an emulsion; carrying out spray drying (220 ℃) treatment on the emulsion to obtain a material precursor; and (3) placing the precursor in a closed quartz tube filled with nitrogen, and treating for 6h at 400 ℃ to obtain the porous carbon-coated mesoporous nano red phosphorus composite material A1. The red phosphorus content of the composite material is determined to be about 75%, the composite material smear is prepared into an electrode, the electrode and a lithium sheet are assembled into a half cell, and the electrochemical performance of the half cell is tested, and the electrochemical performance is shown in figure 3 and table 1.
As shown in FIG. 2, the synthesized red phosphorus particles are nano-sized and have uniform particle size, and the nano-red phosphorus contains a large amount of mesoporous structures therein, and the pore size is about 2-5 nm. As can be seen from FIG. 3, the first charge-discharge specific capacity of the prepared porous carbon-coated mesoporous nano red phosphorus composite negative electrode material is higher than 1800 mAh.g-1After 300 times of circulation, the discharge specific capacity still remains 1425mAh g-1Namely, the composite negative electrode material has very excellent specific discharge capacity and cycle performance.
Example 2
The difference from the above example 1 is that the preparation method is as follows: grinding 400mg of micron-sized red phosphorus for 20min, putting the ground red phosphorus into a closed reactor, adding 25mL of butanediamine and 5mL of propylene glycol, and performing ultrasonic treatment for 30 min; and (3) placing the mixture into a thermostat to react for 12 hours at 250 ℃, cooling to normal temperature after the reaction is finished, standing, centrifuging and drying to obtain the mesoporous nano red phosphorus particles. Mixing 300mg of nano red phosphorus particles, 250mg of glucose and 2.5mg of nickel chloride, and performing high-speed shearing and emulsification to prepare an emulsion; carrying out spray drying (200 ℃) treatment on the emulsion to obtain a material precursor; and (3) placing the precursor in a closed quartz tube filled with nitrogen, and treating for 2h at 350 ℃ to obtain the porous carbon-coated mesoporous nano red phosphorus composite material A2. The red phosphorus content in the composite material is determined to be about 75%, the composite material smear is prepared into an electrode, the electrode and a lithium sheet are assembled into a half cell, the electrochemical performance of the half cell is tested, and the data is shown in table 1.
Example 3
Grinding 400mg of micron-sized red phosphorus for 20min, putting the ground red phosphorus into a closed reactor, adding 25mL of hexamethylene diamine and 5mL of ethylene glycol, and carrying out ultrasonic treatment for 30 min; and (3) placing the mixture into a thermostat to react for 36 hours at the temperature of 150 ℃, cooling the mixture to normal temperature after the reaction is finished, standing, centrifuging and drying the mixture to obtain the mesoporous nano red phosphorus particles. Mixing 300mg of nano red phosphorus particles with 350mg of polypyrrole and 7mg of ferrocene, and performing high-speed shearing and emulsification to prepare an emulsion; carrying out spray drying (120 ℃) treatment on the emulsion to obtain a material precursor; and (3) placing the precursor in a closed quartz tube filled with nitrogen, and treating for 8 hours at 300 ℃ to obtain the porous carbon-coated mesoporous nano red phosphorus composite material A3. The red phosphorus content in the composite material is determined to be 75%, the composite material smear is prepared into an electrode, the electrode and a lithium sheet are assembled into a half cell, the electrochemical performance of the half cell is tested, and the data is shown in table 1.
Example 4
Grinding 400mg of micron-sized red phosphorus for 20min, putting the ground red phosphorus into a closed reactor, adding 25mL of triethanolamine and 5mL of isopropanol, and carrying out ultrasonic treatment for 30 min; and (3) placing the mixture into a thermostat to react for 24 hours at 200 ℃, cooling to normal temperature after the reaction is finished, standing, centrifuging and drying to obtain the mesoporous nano red phosphorus particles. Mixing 300mg of nano red phosphorus particles, 150mg of vitamin C and 3mg of cobaltocene, and carrying out high-speed shearing emulsification to prepare an emulsion; carrying out spray drying (220 ℃) treatment on the emulsion to obtain a material precursor; and (3) placing the precursor in a closed quartz tube filled with nitrogen, and treating for 6h at 400 ℃ to obtain the porous carbon-coated mesoporous nano red phosphorus composite material A4. The red phosphorus content in the composite material is determined to be about 85%, the composite material smear is prepared into an electrode, the electrode and a lithium sheet are assembled into a half cell, and the electrochemical performance of the half cell is tested, which is shown in table 1.
Example 5
Grinding 400mg of micron-sized red phosphorus for 20min, putting the ground red phosphorus into a closed reactor, adding 25mL of propylene diamine and 5mL of ethylene glycol, and carrying out ultrasonic treatment for 30 min; and (3) placing the mixture into a thermostat to react for 24 hours at 200 ℃, cooling to normal temperature after the reaction is finished, standing, centrifuging, washing and drying to obtain the mesoporous nano red phosphorus particles. Mixing 300mg of nano red phosphorus particles, 800mg of glucose and 24mg of nickel cyclopentadienyl, and carrying out high-speed shearing emulsification to prepare an emulsion; carrying out spray drying (220 ℃) treatment on the emulsion to obtain a material precursor; and (3) placing the precursor in a closed quartz tube filled with nitrogen, and treating for 6h at 380 ℃ to obtain the porous carbon-coated mesoporous nano red phosphorus composite material A5. The red phosphorus content in the composite material is determined to be about 50%, the composite material smear is prepared into an electrode, the electrode and a lithium sheet are assembled into a half cell, and the electrochemical performance of the half cell is tested, which is shown in table 1.
Comparative example 1
Grinding 400mg of micron-sized red phosphorus for 20min, putting the ground red phosphorus into a closed reactor, adding 25mL of propylene diamine and 5mL of ethylene glycol, and carrying out ultrasonic treatment for 30 min; and (3) placing the obtained product into a thermostat to react for 24 hours at 200 ℃, cooling to normal temperature after the reaction is finished, standing, centrifuging and drying to obtain a mesoporous nano red phosphorus material D1, preparing a D1 smear into an electrode, assembling the electrode and a lithium sheet into a half cell, and testing the electrochemical performance of the half cell, wherein the data are shown in Table 1.
Comparative example 2
Grinding 400mg of micron-sized red phosphorus for 20min, mixing with 320mg of sucrose and 6.4mg of ferrocene, and performing high-speed shearing and emulsification to prepare an emulsion; carrying out spray drying (220 ℃) treatment on the emulsion to obtain a material precursor; and (3) placing the precursor in a closed quartz tube filled with nitrogen for treatment at 400 ℃ for 6h to obtain the red phosphorus/carbon composite material D2. The red phosphorus content in the composite material is determined to be about 75%, the composite material smear is prepared into an electrode, the electrode and a lithium sheet are assembled into a half cell, the electrochemical performance of the half cell is tested, and the data is shown in table 1.
Comparative example 3
Grinding 400mg of micron-sized red phosphorus for 20min, mixing with 320mg of sucrose and 6.4mg of ferrocene, filtering, and performing heat treatment at 400 ℃ for 6h in a closed quartz tube filled with nitrogen to obtain the red phosphorus/carbon composite material D3. The red phosphorus content in the composite material is determined to be about 75%, the composite material smear is prepared into an electrode, the electrode and a lithium sheet are assembled into a half cell, the electrochemical performance of the half cell is tested, and the data is shown in table 1.
TABLE 1 electrochemical Properties of the materials of the examples and the comparative examples
From table 1, it can be seen that the porous carbon-coated mesoporous red phosphorus composite material a1-a4 prepared by the invention has excellent specific discharge capacity and cycle stability, and the electrochemical performance of the composite material is significantly better than that of the comparative example material D1-D3, and in addition, the sample a5 shows that the red phosphorus content in the composite material can be adjusted as required, and the composite material still has excellent electrochemical performance under the condition of low red phosphorus content.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (9)
1. The lithium ion battery cathode composite material is characterized in that: the composite material is formed by superposing a plurality of spherical nanoscale red phosphorus and carbon primary particles to form micron-sized spherical secondary particles, wherein the nanoscale red phosphorus and carbon primary particles are uniformly coated on the surfaces of the nano red phosphorus particles by a carbon layer, the carbon layer is of a porous structure, the nano red phosphorus particles are of a mesoporous structure, and a gap microstructure is formed between the carbon layer and the nano red phosphorus particles.
2. The preparation method of the porous carbon-coated mesoporous red phosphorus composite material according to claim 1, characterized by comprising the following steps:
(1) uniformly mixing commercial red phosphorus, organic amine and an alcohol additive, reacting under certain process conditions, standing, centrifuging, washing and drying to obtain mesoporous nano red phosphorus particles, wherein the mixing ratio of the commercial red phosphorus to the organic amine to the alcohol additive is 400 mg: 25mL of: 5 mL;
(2) mixing the mesoporous nano red phosphorus obtained in the step (1) with an organic carbon source and a carbonizing agent, and performing high-speed shearing and emulsification to prepare an emulsion, wherein the mass ratio of the mesoporous nano red phosphorus to the organic carbon source is 1: 0.2-5, wherein the mass ratio of the organic carbon source to the carbonizing agent is 1: 0.01-0.03;
(3) placing the emulsion obtained in the step (2) into a spray dryer, and performing spray drying treatment to obtain a precursor of the porous carbon-coated mesoporous red phosphorus material;
(4) and (4) placing the precursor obtained in the step (3) into a closed quartz tube filled with inert gas, and roasting at low temperature to obtain the porous carbon-coated mesoporous red phosphorus active composite material.
3. The preparation method of the porous carbon-coated mesoporous red phosphorus composite material according to claim 2, characterized by comprising the following steps: the process conditions in the step (1) are that the reaction temperature is 150 ℃ and 250 ℃ and the time is 12-36 h.
4. The preparation method of the porous carbon-coated mesoporous red phosphorus composite material according to claim 2, characterized by comprising the following steps: the organic ammonium solution in the step (1) is one or more of propane diamine, butane diamine, hexane diamine and triethanolamine.
5. The preparation method of the porous carbon-coated mesoporous red phosphorus composite material according to claim 2, characterized by comprising the following steps: the alcohol additive in the step (1) is one or more of ethylene glycol, propylene glycol and isopropanol.
6. The preparation method of the porous carbon-coated mesoporous red phosphorus composite material according to claim 2, characterized by comprising the following steps: the organic carbon source in the step (2) is one or more of sucrose, glucose, vitamin C and polypyrrole.
7. The preparation method of the porous carbon-coated mesoporous red phosphorus composite material according to claim 2, characterized by comprising the following steps: the carbonizing agent in the step (2) is one or more of ferrocene, nickelocene and cobaltocene.
8. The preparation method of the porous carbon-coated mesoporous red phosphorus composite material according to claim 2, characterized by comprising the following steps: the temperature of the spray drying in the step (3) is 120-220 ℃.
9. The preparation method of the porous carbon-coated mesoporous red phosphorus composite material according to claim 2, characterized by comprising the following steps: the low-temperature roasting condition in the step (4) is 300-400 ℃, and the time is 2-8 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116759564A (en) * | 2023-08-22 | 2023-09-15 | 深圳海辰储能控制技术有限公司 | Negative electrode composite material, preparation method thereof, negative electrode plate and battery |
| CN116759529A (en) * | 2023-08-22 | 2023-09-15 | 深圳海辰储能控制技术有限公司 | Negative electrode composite material, preparation method thereof, negative electrode plate and battery |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784696A (en) * | 2016-12-26 | 2017-05-31 | 深圳市贝特瑞纳米科技有限公司 | A kind of titanium phosphate sodium/carbon composite, Preparation Method And The Use |
| CN107317008A (en) * | 2017-06-20 | 2017-11-03 | 大连理工常州研究院有限公司 | The preparation method and application of core-shell type carbon-clad metal phosphide nano-complex particle |
| CN107681126A (en) * | 2016-08-02 | 2018-02-09 | 清华大学 | Phosphorus carbon composite, the battery of its preparation method and application the phosphorus carbon composite |
| CN108695496A (en) * | 2018-04-27 | 2018-10-23 | 厦门稀土材料研究所 | The porous red phosphorus of graphene coated, conductive carbon composite, preparation method and application |
| CN109216682A (en) * | 2018-09-25 | 2019-01-15 | 桑德集团有限公司 | A kind of phosphorus base negative electrode material and preparation method thereof, cathode and lithium ion battery |
| CN109309199A (en) * | 2017-07-26 | 2019-02-05 | 中国地质大学（北京） | A kind of negative electrode of lithium ion battery red phosphorus/carbon nano tube compound material preparation method |
| CN110165191A (en) * | 2019-06-11 | 2019-08-23 | 武汉理工大学 | A kind of air-stable type red phosphorus base composite negative pole material and preparation method thereof |
| CN111211308A (en) * | 2020-01-15 | 2020-05-29 | 东莞理工学院 | Loofah sponge biomass carbon-loaded red phosphorus lithium ion battery negative electrode material and preparation method thereof |
| WO2020146630A1 (en) * | 2019-01-10 | 2020-07-16 | The Board Of Trustees Of The Leland Stanford Junior University | Red phosphorus/carbon nanocomposite as high capacity and fast-charging battery anode material |
| CN111785946A (en) * | 2020-07-23 | 2020-10-16 | 苏州大学 | Negative active material, preparation and application thereof |
| CN112420999A (en) * | 2020-10-13 | 2021-02-26 | 天津大学 | Phosphorus-based negative electrode material with coating structure and preparation method and application thereof |
-
2021
- 2021-10-18 CN CN202111209610.9A patent/CN113839026B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107681126A (en) * | 2016-08-02 | 2018-02-09 | 清华大学 | Phosphorus carbon composite, the battery of its preparation method and application the phosphorus carbon composite |
| CN106784696A (en) * | 2016-12-26 | 2017-05-31 | 深圳市贝特瑞纳米科技有限公司 | A kind of titanium phosphate sodium/carbon composite, Preparation Method And The Use |
| CN107317008A (en) * | 2017-06-20 | 2017-11-03 | 大连理工常州研究院有限公司 | The preparation method and application of core-shell type carbon-clad metal phosphide nano-complex particle |
| CN109309199A (en) * | 2017-07-26 | 2019-02-05 | 中国地质大学（北京） | A kind of negative electrode of lithium ion battery red phosphorus/carbon nano tube compound material preparation method |
| CN108695496A (en) * | 2018-04-27 | 2018-10-23 | 厦门稀土材料研究所 | The porous red phosphorus of graphene coated, conductive carbon composite, preparation method and application |
| CN109216682A (en) * | 2018-09-25 | 2019-01-15 | 桑德集团有限公司 | A kind of phosphorus base negative electrode material and preparation method thereof, cathode and lithium ion battery |
| WO2020146630A1 (en) * | 2019-01-10 | 2020-07-16 | The Board Of Trustees Of The Leland Stanford Junior University | Red phosphorus/carbon nanocomposite as high capacity and fast-charging battery anode material |
| CN110165191A (en) * | 2019-06-11 | 2019-08-23 | 武汉理工大学 | A kind of air-stable type red phosphorus base composite negative pole material and preparation method thereof |
| CN111211308A (en) * | 2020-01-15 | 2020-05-29 | 东莞理工学院 | Loofah sponge biomass carbon-loaded red phosphorus lithium ion battery negative electrode material and preparation method thereof |
| CN111785946A (en) * | 2020-07-23 | 2020-10-16 | 苏州大学 | Negative active material, preparation and application thereof |
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| CN116759564A (en) * | 2023-08-22 | 2023-09-15 | 深圳海辰储能控制技术有限公司 | Negative electrode composite material, preparation method thereof, negative electrode plate and battery |
| CN116759529A (en) * | 2023-08-22 | 2023-09-15 | 深圳海辰储能控制技术有限公司 | Negative electrode composite material, preparation method thereof, negative electrode plate and battery |
| CN116759529B (en) * | 2023-08-22 | 2024-01-12 | 深圳海辰储能控制技术有限公司 | Negative electrode composite material, preparation method thereof, negative electrode plate and battery |
| CN116759564B (en) * | 2023-08-22 | 2024-02-13 | 深圳海辰储能控制技术有限公司 | Negative electrode composite material, preparation method thereof, negative electrode plate and battery |
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