CN113363464A - Gallium-silicon-phosphorus composite negative electrode active material, lithium ion battery, and preparation method and application thereof - Google Patents
Gallium-silicon-phosphorus composite negative electrode active material, lithium ion battery, and preparation method and application thereof Download PDFInfo
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- 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
- H01M4/5805—Phosphides
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- 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
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- 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
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention provides a gallium-silicon-phosphorus composite negative electrode active material, a lithium ion battery, and a preparation method and application thereof. The gallium silicon phosphorus composite cathode active material has a ZnS type crystal structure and has a chemical formula of GaSiXPX+1In the formula, 0<X is less than or equal to 4. The composite material has a stable ZnS structure, P occupies an anion position, Si and Ga occupy a cation position, and the doping structure ensures that the prepared lithium ion battery not only has higher first cycle efficiency and specific capacity, but also has good cycle stability, and after 100 cycles of cycle, the capacity retention rate is up to 89.1%, and is improved by 35.8% compared with pure GaP.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a gallium-silicon-phosphorus composite negative active material, a lithium ion battery, and a preparation method and application thereof.
Background
In order to solve the problems of shortage of fossil energy and environmental pollution, the search for new clean energy to replace the existing energy is urgent. However, these clean energy sources (such as wind energy, tidal energy, solar energy, water energy, geothermal energy, etc.) have a significant drawback of timeliness and do not create a continuous energy output. Based on this, energy storage devices are produced. Among the numerous energy storage devices, lithium ion batteries have the advantages of highest energy density, environmental friendliness, no memory effect, light weight, small size and the like, are considered as the preferred power source, and have successfully been commercialized in 1991. The battery is composed of a positive electrode material, an electrolyte, a diaphragm and a negative electrode material, wherein the positive electrode material and the negative electrode material are the important materials of the battery, so the improvement of the positive electrode material and the negative electrode material is needed to be started in order to improve the energy storage technology.
The current commercial lithium ion battery takes graphite as a negative electrode material, but the theoretical specific capacity of the lithium ion battery is only 372mAhg-1The lithium storage potential is low, dendrite is easy to generate, great potential safety hazard is possessed, the commercial use of the existing graphite carbon material is close to the theoretical capacity, and the higher capacity requirement is difficult to achieve, so the research of the cathode material is the key for improving the capacity and the energy density of the lithium ion battery.
In order to overcome the limitation of graphite in specific capacity and the safety problem, researchers are dedicated to develop negative electrode materials with higher capacity and higher lithium intercalation potential (such as chinese patents CN111276692A and CN 104600299A). Among them, silicon (Si), phosphorus (P), and germanium (Ge) are widely paid attention to, and the respective theoretical specific capacities are 4200mAhg-1、2596mAhg-1、1600mAhg-1. However, this type of material undergoes a series of irreversible structural changes and huge volume expansion during lithium storage, resulting in cracking, pulverization and detachment of the electrode material from the current collector, resulting in poor cycle stability of the battery, which seriously hinders the practical application of this type of alloy type negative electrode material in a full battery.
Therefore, it is desirable to provide a negative electrode material with high capacity, high first coulombic efficiency, and good cycle stability.
Disclosure of Invention
The invention aims to overcome the defect of poor cycle stability of a lithium ion battery cathode material in the prior art, and provides a gallium-silicon-phosphorus composite cathode active material which has high capacity, high first coulombic efficiency and good cycle stability.
The invention also aims to provide a preparation method of the gallium silicon phosphorus composite negative active material.
The invention also aims to provide application of the gallium silicon phosphorus composite negative electrode active material in preparation of a lithium ion battery.
The invention also aims to provide a lithium ion battery prepared from the gallium-silicon-phosphorus composite negative active material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the gallium-silicon-phosphorus composite negative active material has a chemical formula of GaSiXPX+1In the formula, 0<X is less than or equal to 4; the gallium silicon phosphorus composite negative electrode active material is of a ZnS type crystal structure, Ga and Si occupy positive ion positions, and P occupies negative ion positions.
Through a great deal of research, the inventor of the invention discovers that GaP with a ZnS type crystal structure (ZnS structure for short) has excellent electrochemical performance, and can improve the lithium ion and electron conduction because the GaP generates Li-Ga alloy with excellent conductivity in the charging and discharging processes; and the GaP has the characteristics of proper working platform, high capacity, high first effect and the like, and the Ga element also has special self-healing performance, so that the Ga element is applied to the lithium ion battery to obtain excellent cycle stability.
But its discharge capacity is only 1220mAhg-1Therefore, it is required to improve specific capacity and first cycle efficiency of GaP, and the inventors of the present invention have previously studied ternary Zn (Ga) -Si-P negative electrode material for lithium ion battery and its storage mechanism [ D ]]Guangdong university of industry, 2020.) some methods have the specific capacity and the first cycle efficiency improved by doping Si element into GaP, and GaP and Si are ball-milled to obtain the gallium-silicon-phosphorus composite material, but the obtained composite material is a solid solution, three elements of gallium-silicon-phosphorus in the crystal structure of the solid solution are on the same site, so that the self-healing performance of the Ga element is influenced, and the cycle stability of the material is still to be improved.
The inventors of the present invention have found, through further studies, that Si and P are doped into the crystal structure of GaPForm with GaSiXPX+1(X is more than 0 and less than or equal to 4) to form a stable ZnS structure (P element occupies an anion position, Ga and Si elements occupy a cation position), and the doped structure can enable the material to have good cycling stability under the condition of improving the specific capacity and the first cycling efficiency of the material.
The charge and discharge performance of the material can be adjusted by adjusting the P, Si content, the P, Si content is too high, and the first coulombic efficiency of the prepared lithium ion battery is reduced; p, Si content is too low, and the initial capacity of the prepared lithium ion battery is smaller. Preferably, in the gallium-silicon-phosphorus composite negative active material, X is more than or equal to 0.1 and less than or equal to 4; more preferably 1. ltoreq. X.ltoreq.3; more preferably, X is 2.
The preparation method of the gallium-silicon-phosphorus composite negative active material comprises the following steps:
and ball-milling the GaP, the P and the Si for 5-7 h under the condition of 1000-1300 r/min in an inert atmosphere environment to obtain the gallium-silicon-phosphorus composite cathode active material.
The invention adopts a high-energy ball milling method, and has simple operation and low cost.
Preferably, the rotation speed of the ball mill is 1200 r/min.
Preferably, the time of the ball milling is 6 h.
Preferably, the inert atmosphere is an atmosphere formed by combining one or more of argon, helium and nitrogen.
Further preferably, the inert atmosphere is an argon atmosphere.
The application of the gallium silicon phosphorus composite negative active material in the preparation of the lithium ion battery is also within the protection scope of the invention.
The invention also protects a lithium ion battery, which consists of a positive electrode, a negative electrode and a diaphragm; the negative electrode comprises the gallium-silicon-phosphorus composite negative electrode active material, a conductive agent, a binder and a current collector.
Materials with conductive property can be used for the conductive agent of the invention, and specifically, the conductive agent is one or a combination of several of acetylene black, natural graphite, artificial graphite, carbon fiber, carbon nanotube, copper powder, copper mesh, metal powder, graphene oxide, reduced graphene oxide, titanium carbide, titanium nitride, polyaniline, polythiophene or polypyrrole.
Any of the commercially available binders and current collectors can be used in the lithium ion battery of the present invention.
Preferably, the binder is one or a combination of polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), polyacrylic acid (PAA), sodium alginate (Alg or SA), Polyamideimide (PAI), lithium polyacrylate (Li-PAA), conductive Polymer (PFM), poly (9,9' -dioctylfluorene-fluorenone-methyl benzoate), polyvinyl alcohol (PVA), Polytetrafluoroethylene (PTFE)64, polyurethane (TPU) or Styrene Butadiene Rubber (SBR).
Preferably, the current collector is one or a combination of copper foil, aluminum foil, nickel foil, copper mesh, copper foam, nickel foam, aluminum mesh or nickel mesh.
Compared with the prior art, the invention has the beneficial effects that:
the invention introduces GaP with semiconductor property, P element with lithium storage activity and Si element into one component to form GaSiXPX+1(X is more than 0 and less than or equal to 4), the composite material has a stable ZnS structure, Si and P are doped into a GaP structure, P occupies an anion position, Si occupies a cation position, the doping structure can improve the first cycle efficiency and specific capacity of the lithium ion battery, and has good cycle stability, after 100 cycles of cycle, the capacity retention rate is up to 89.1%, and the capacity retention rate is improved by 35.8% compared with pure GaP.
Drawings
FIG. 1 is a schematic diagram of the positions of elements in a unit cell of a gallium-silicon-phosphorus composite negative active material prepared in examples 1 to 4;
FIG. 2 is an XRD spectrum of a gallium-silicon-phosphorus composite negative active material prepared in examples 1 to 4;
fig. 3 is an XRD spectrum of the GaSiP composite negative active material prepared in comparative example 2;
FIG. 4 is a graph obtained by preparing comparative example 3GeSiP of2An XRD spectrum of the composite negative active material;
FIG. 5 is a charge-discharge curve diagram of a lithium ion battery prepared by using the gallium-silicon-phosphorus composite negative active material prepared in example 1;
FIG. 6 is a charge-discharge curve diagram of a lithium ion battery prepared by using the gallium-silicon-phosphorus composite negative active material prepared in example 2;
FIG. 7 is a charge-discharge curve diagram of a lithium ion battery prepared by using the gallium-silicon-phosphorus composite negative active material prepared in example 3;
FIG. 8 shows GaSiP2、GaSi2P3、GaSi3P4Preparing a first circle of electrochemical curve of the obtained lithium ion battery;
FIG. 9 is GaSiP of example 12Electrochemical graphs of 100 cycles of lithium ion batteries prepared from GaP of comparative example 1;
fig. 10 is a first turn electrochemical curve of a lithium ion battery prepared from the GaSiP of comparative example 2.
Detailed Description
The present invention will be further described with reference to the following specific examples and drawings, which are not intended to limit the invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
Example 1
This example provides a gallium-silicon-phosphorus composite cathode active material with a chemical formula of GaSiP2The preparation method comprises the following steps:
placing GaP, P and Si into a ball milling tank according to a chemical weight ratio (namely a molar ratio of 1:1:1), then adding stainless steel balls (the ball material mass ratio is 20:1), then filling argon into a glove box, sealing after filling, performing interval of 25min every 1h of ball milling, rotating speed of 1200r, performing unidirectional rotation, performing total ball milling for 6h, and taking materials in the glove box after ball milling to obtain GaSiP2A composite anode active material.
For the prepared GaSiP2The XRD structure of the composite cathode active material is characterized, and the result is shown in figure 2, which shows that GaSiP2The main peak position of XRD of the material is the same as that of GaP, and the peak intensity is similar, which shows that the GaSiP prepared by high-energy ball milling method2Has the same crystal structure as GaP, namely has a stable ZnS structure (the structural diagram is shown in FIG. 1), and P element occupies anion position and Ga and Si element occupy cation position.
Example 2
This example provides a gallium-silicon-phosphorus composite cathode active material with a chemical formula of GaSi2P3The difference between the preparation method and the embodiment 1 is that the mol ratio of GaP, P and Si is 1:2: 2. GaSi2P3The XRD spectrum of the composite anode active material is shown in fig. 2.
Example 3
This example provides a gallium-silicon-phosphorus composite cathode active material with a chemical formula of GaSi3P4The difference between the preparation method and the embodiment 1 is that the mol ratio of GaP, P and Si is 1:3: 3. GaSi3P4The XRD spectrum of the composite anode active material is shown in fig. 2.
Example 4
This example provides a gallium-silicon-phosphorus composite cathode active material with a chemical formula of GaSi4P5The difference between the preparation method and the embodiment 1 is that the mol ratio of GaP, P and Si is 1:4: 4. GaSi4P5The XRD spectrum of the composite anode active material is shown in fig. 2.
Example 5
This example provides a gallium-silicon-phosphorus composite cathode active material with a chemical formula of GaSi0.1P1.1The difference between the preparation method and the embodiment 1 is that the mol ratio of GaP, P and Si is 1:0.1: 0.1. GaSi0.1P1.1The XRD pattern of the composite negative active material is similar to that of examples 1-4.
Comparative example 1
This comparative example is gallium phosphide (GaP).
Comparative example 2
The comparative example provides a gallium-silicon-phosphorus composite negative active material, which is different from example 1 in that P is not added, the chemical formula of the prepared composite material is GaSiP, and the XRD spectrum of the composite material is shown in figure 3.
Comparative example 3
This comparative example provides a composite anode active material, which is different from example 1 in that GaP was replaced with GeP, and the chemical formula of the prepared composite material was GeSiP2The XRD pattern is shown in figure 4.
The negative active materials prepared in the above examples and comparative examples were prepared into lithium ion batteries (2032 lithium ion button half cells), and their electrochemistry was tested.
Preparing a lithium ion battery:
s1, preparation of negative electrode plate
Taking 700mg of the negative electrode active material prepared in the embodiment or the comparative example, 200mg of conductive agent acetylene black and 100mg of binder Li-PAA (the negative electrode active material: the conductive agent: the binder is 7:2:1) to grind (manual grinding can be selected, and a magnetic rotor can be selected to uniformly mix), wherein the mixing step needs to be noticed that the active material and the acetylene black are firstly mixed, then the binder is added to uniformly mix, and the uniform mixing time of the materials can be adjusted according to the amount of the materials and can be uniformly mixed); coating the uniformly mixed mixture on a Cu foil (current collector), drying for 8h at 70 ℃, slicing (a wafer with the diameter of 10 mm), and tabletting to obtain an electrode plate;
s2. preparation of electrolyte
LiPF6Dissolving in mixed solvent of EC, DMC and EMC at a volume ratio of 1:1:1, LiPF6The concentration of (2) is 1mol/L, and an additive VC which is helpful for film formation is added, wherein the adding proportion is 2 wt%.
S3.2032 lithium ion button half cell assembly
2032 button half-cells are assembled in a glove box with water and oxygen content less than 0.1 ppm. S1, placing the electrode plate obtained in the positive center of a battery case, contacting copper foil with stainless steel, adding 2-3 drops of the electrolyte obtained in S2 by using a dropper, then placing a diaphragm on the electrode plate, adding 1-2 drops of the electrolyte in the center of the diaphragm by using the dropper, then placing a lithium plate on diaphragm paper, sequentially placing a gasket, an elastic sheet and a negative electrode case, and packaging by using a sealing machine, namely assembling the 2032 button type half battery.
Electrochemical performance test
The battery assembled by the method adopts a voltage control constant current charge-discharge mode, and the charge-discharge current density is 100mAg-1The charging and discharging voltage range is 0.005-3.0V.
The test results are shown in Table 1 and FIGS. 5 to 8.
TABLE 1 electrochemical Performance test results
As can be seen from Table 1 and FIGS. 5 to 9, the GaSi of the present inventionXPX+1(X is more than 0 and less than or equal to 4), compared with pure GaP (comparative example 1), the initial capacity, the first cycle efficiency and the cycle stability (capacity retention rate after 100 cycles) of the composite cathode active material are improved. Wherein the initial capacity is increased by at least 21.3% and the first cycle efficiency is increased by at least 10%.
As can be seen from fig. 9, the cycling stability of the composite anode active material of example 1 is significantly higher than that of pure GaP (comparative example 1), the specific capacity of the material starts to be significantly reduced after 70 cycles of pure GaP, while the specific capacity of the material of example 1 of the present invention can still be kept stable after 100 cycles, the capacity can be kept at 89.1%, which is significantly higher than that of pure GaP (capacity retention ratio is 65.5% after 100 cycles of cycles), and the capacity retention ratio is improved by 35.8%. The graph of the other examples was similar to example 1 with 100 cycles of charge and discharge. The material of comparative example 2 is a solid solution structure, and the capacity retention rate of the lithium ion battery prepared by the material can only reach 83% after 50 cycles, which is significantly lower than that of the invention; comparative example 3 a mixture was prepared, and the capacity retention of the lithium ion battery prepared therefrom was only 75% after 50 cycles.
From FIG. 8 (GaSiP)2、GaSi2P3、GaSi3P4The first circle of electrochemical curve comparison) shows that the specific capacity of the prepared lithium ion battery is increased along with the increase of the doping amount (namely, the X value) of Si and P, but the first coulombic efficiency is weakened to the optimization of GaP.
The comparative example 2 is not doped with P element, only Si is added, and it can be seen from the XRD spectrum (fig. 3) of the prepared active material that the characteristic peak intensity of GaSiP is lower than that of GaP, and the peak in the range of 27 to 29 ° shifts toward the Si peak, indicating that the crystal structure contains characteristic peaks of Si and GaP, in which Si is doped into GaP in a solid solution manner, and the initial specific capacity and the first turn coulombic efficiency of the lithium ion battery prepared by using the same are inferior to those of the embodiment of the present invention (fig. 10).
In comparative example 3, when Ga was replaced with Ge, it was found that the XRD spectrum (as shown in fig. 4) of the prepared composite electrode active material had no distinct GeP peak, and it was found that the composite material formed was a mixture and did not have a ZnS structure. Therefore, the initial specific capacity and the first-turn coulombic efficiency of the lithium ion battery prepared by using the lithium ion battery are poor.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The gallium-silicon-phosphorus composite negative active material is characterized in that the chemical formula of the gallium-silicon-phosphorus composite negative active material is GaSiXPX+1In the formula, 0<X is less than or equal to 4; the gallium silicon phosphorus composite negative electrode active material is of a ZnS type crystal structure, Ga and Si occupy positive ion positions, and P occupies negative ion positions.
2. The gallium silicon phosphorus composite anode active material according to claim 1, wherein X is 0.1. ltoreq. X.ltoreq.4.
3. The gallium silicon phosphorus composite anode active material according to claim 2, wherein X is 1. ltoreq. X.ltoreq.3.
4. The method for preparing the gallium silicon phosphorus composite negative active material of any one of claims 1 to 3, characterized by comprising the following steps:
and ball-milling the GaP, the P and the Si for 5-7 h under the condition of 1000-1300 r/min in an inert atmosphere environment to obtain the gallium-silicon-phosphorus composite cathode active material.
5. The preparation method of the gallium silicon phosphorus composite negative active material as claimed in claim 4, wherein the rotation speed of the ball milling is 1200 r/min.
6. The preparation method of the gallium silicon phosphorus composite anode active material as claimed in claim 4, wherein the ball milling time is 6 h.
7. The method for preparing the gallium-silicon-phosphorus composite anode active material according to claim 4, wherein the inert atmosphere is one or a combination of argon, helium and nitrogen.
8. The method for preparing the gallium, silicon and phosphorus composite anode active material according to claim 7, wherein the inert atmosphere is an argon atmosphere.
9. The use of a gallium, silicon and phosphorus composite anode active material according to any one of claims 1 to 3 in the preparation of lithium ion batteries.
10. The lithium ion battery is characterized by comprising a positive electrode, a negative electrode and a diaphragm; the negative electrode comprises the gallium silicon phosphorus composite negative active material, a conductive agent, a binder and a current collector according to any one of claims 1 to 3.
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3943016A (en) * | 1970-12-07 | 1976-03-09 | General Electric Company | Gallium-phosphorus simultaneous diffusion process |
| JPH0786503A (en) * | 1993-09-19 | 1995-03-31 | Hiroyasu Hirano | Alsip mixed crystal three-dimensional integrated circuit |
| US5770333A (en) * | 1995-06-12 | 1998-06-23 | Hitachi, Ltd. | Nonaqueous secondary battery and negative electrode material therefor |
| CN1482207A (en) * | 2003-07-28 | 2004-03-17 | 中国科学技术大学 | Water heat systhesis method for preparing phosphide nanometre wire |
| US20050258368A1 (en) * | 2004-05-19 | 2005-11-24 | Aisin Seiki Kabushiki Kaisha | Semiconductor crystal for generating terahertz waves, terahertz wave-generator incorporating the crystal, semiconductor crystal for detecting terahertz waves, and terahertz waves detector incorporating the crystal |
| CN1996613A (en) * | 2000-08-22 | 2007-07-11 | 哈佛学院董事会 | Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors and fabricating such devices |
| US20100209775A1 (en) * | 2009-02-16 | 2010-08-19 | Samsung Electronics Co., Ltd | Negative electrode including group 14 metal/metalloid nanotubes, lithium battery including the negative electrode, and method of manufacturing the negative electrode |
| CN101964417A (en) * | 2009-07-22 | 2011-02-02 | 巴莱诺斯清洁能源控股公司 | New electrode material is particularly useful for the new electrode material of rechargable lithium ion cell |
| CN102428763A (en) * | 2009-05-19 | 2012-04-25 | 纳米***公司 | Nanostructured materials for battery applications |
| CN103579592A (en) * | 2012-08-03 | 2014-02-12 | 信越化学工业株式会社 | Silicon-containing particles, negative electrode material for nonaqueous electrolyte secondary battery using the same, nonaqueous electrolyte secondary battery, and method of manufacturing silicon-containing particles |
| CN104137308A (en) * | 2012-02-28 | 2014-11-05 | 奈克松有限公司 | Structured silicon particles |
| CN104600299A (en) * | 2015-01-08 | 2015-05-06 | 华中科技大学 | Negative electrode active material for lithium-ion/sodium-ion battery, negative electrode and battery |
| CN106784749A (en) * | 2017-03-21 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of silicon black phosphorus liquid metal ternary lithium cell cathode material and preparation method |
| CN107858754A (en) * | 2017-11-07 | 2018-03-30 | 国家纳米科学中心 | A kind of GaP nano wires and its production and use |
| CN109873130A (en) * | 2017-12-04 | 2019-06-11 | 广东工业大学 | A kind of lithium ion/sodium-ion battery polynary full active cathode material, cathode and battery |
| CN111129491A (en) * | 2019-12-20 | 2020-05-08 | 广东工业大学 | Lithium ion battery negative electrode active material, preparation method thereof and lithium ion battery |
-
2021
- 2021-06-08 CN CN202110640423.XA patent/CN113363464A/en active Pending
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3943016A (en) * | 1970-12-07 | 1976-03-09 | General Electric Company | Gallium-phosphorus simultaneous diffusion process |
| JPH0786503A (en) * | 1993-09-19 | 1995-03-31 | Hiroyasu Hirano | Alsip mixed crystal three-dimensional integrated circuit |
| US5770333A (en) * | 1995-06-12 | 1998-06-23 | Hitachi, Ltd. | Nonaqueous secondary battery and negative electrode material therefor |
| CN1996613A (en) * | 2000-08-22 | 2007-07-11 | 哈佛学院董事会 | Doped elongated semiconductors, growing such semiconductors, devices including such semiconductors and fabricating such devices |
| CN1482207A (en) * | 2003-07-28 | 2004-03-17 | 中国科学技术大学 | Water heat systhesis method for preparing phosphide nanometre wire |
| US20050258368A1 (en) * | 2004-05-19 | 2005-11-24 | Aisin Seiki Kabushiki Kaisha | Semiconductor crystal for generating terahertz waves, terahertz wave-generator incorporating the crystal, semiconductor crystal for detecting terahertz waves, and terahertz waves detector incorporating the crystal |
| US20100209775A1 (en) * | 2009-02-16 | 2010-08-19 | Samsung Electronics Co., Ltd | Negative electrode including group 14 metal/metalloid nanotubes, lithium battery including the negative electrode, and method of manufacturing the negative electrode |
| CN102428763A (en) * | 2009-05-19 | 2012-04-25 | 纳米***公司 | Nanostructured materials for battery applications |
| CN101964417A (en) * | 2009-07-22 | 2011-02-02 | 巴莱诺斯清洁能源控股公司 | New electrode material is particularly useful for the new electrode material of rechargable lithium ion cell |
| CN104137308A (en) * | 2012-02-28 | 2014-11-05 | 奈克松有限公司 | Structured silicon particles |
| CN103579592A (en) * | 2012-08-03 | 2014-02-12 | 信越化学工业株式会社 | Silicon-containing particles, negative electrode material for nonaqueous electrolyte secondary battery using the same, nonaqueous electrolyte secondary battery, and method of manufacturing silicon-containing particles |
| CN104600299A (en) * | 2015-01-08 | 2015-05-06 | 华中科技大学 | Negative electrode active material for lithium-ion/sodium-ion battery, negative electrode and battery |
| CN106784749A (en) * | 2017-03-21 | 2017-05-31 | 成都新柯力化工科技有限公司 | A kind of silicon black phosphorus liquid metal ternary lithium cell cathode material and preparation method |
| CN107858754A (en) * | 2017-11-07 | 2018-03-30 | 国家纳米科学中心 | A kind of GaP nano wires and its production and use |
| CN109873130A (en) * | 2017-12-04 | 2019-06-11 | 广东工业大学 | A kind of lithium ion/sodium-ion battery polynary full active cathode material, cathode and battery |
| CN111129491A (en) * | 2019-12-20 | 2020-05-08 | 广东工业大学 | Lithium ion battery negative electrode active material, preparation method thereof and lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| VO PHAM HOANG HUY ET AL.: "Self-healing gallium phosphide embedded in a hybrid matrix for high-performance Li-ion batteries", 《ENERGY STORAGE MATERIALS》 * |
| WENWU LI ET AL.: "Zn(Cu)Si2+xP3 Solid Solution Anodes for High-Performance Li-Ion Batteries with Tunable Working Potentials", 《ADVANCED FUNCTIONAL MATERIALS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114203965A (en) * | 2021-12-07 | 2022-03-18 | 远景动力技术(江苏)有限公司 | Electrochemical device and electronic apparatus |
| CN114203965B (en) * | 2021-12-07 | 2024-01-30 | 远景动力技术(江苏)有限公司 | Electrochemical device and electronic apparatus |
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