CN109244539A - Organic-inorganic composite solid electrolyte material and its preparation method and application - Google Patents
Organic-inorganic composite solid electrolyte material and its preparation method and application Download PDFInfo
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- CN109244539A CN109244539A CN201811240261.5A CN201811240261A CN109244539A CN 109244539 A CN109244539 A CN 109244539A CN 201811240261 A CN201811240261 A CN 201811240261A CN 109244539 A CN109244539 A CN 109244539A
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present embodiments relate to a kind of Organic-inorganic composite solid electrolyte materials and its preparation method and application, preparation method includes: that polymeric matrix, sodium salt and inorganic electrolyte powder are stocked up according to mass ratio x:(100-x-y): y proportion, and is dried in vacuo 4 hours~12 hours at 100 DEG C~200 DEG C respectively；Wherein x>=60, y>=5, and x+y<100；Inorganic electrolyte powder is added in organic solvent and is dispersed, and is stirred under vacuum 2~4 hours, the first mixture is obtained；Polymeric matrix is added in first mixture, is stirred under vacuum 0.5~2 hour, is dissolved in polymeric matrix in first mixture, obtains the second mixture；Sodium salt is added in second mixture, is stirred under vacuum 4~8 hours, obtains solid electrolyte slurry；Solid electrolyte slurry is poured into film die, solvent is heated at 60 DEG C~80 DEG C and volatilizees completely, then is dried in vacuo 4~12 hours at 100 DEG C~120 DEG C, to obtain Organic-inorganic composite solid electrolyte material.
Description
Technical field
The present invention relates to sodium-ion battery technical field more particularly to a kind of Organic-inorganic composite solid electrolyte materials
And its preparation method and application.
Background technique
Lithium ion battery with its high-energy density, long circulation life, memory-less effect, can be quickly charged and discharged and environmental-friendly
The advantages that, it has attracted attention always since putting goods on the market, in consumption electronic products such as 3C Product, electric tool, electric bicycles
Field occupies leading position.In recent years, the development prospect to attract people's attention is also shown in power battery and energy-storage battery field.
However, tellurian lithium resource is very poor, abundance of the lithium in the earth's crust is only 0.0065%, and distributed pole is not
Uniformly, with the following electric car, the arrival in smart grid epoch, lithium necessarily becomes system because of high price caused by scarcity of resources
An important factor for about it develops, therefore, it is necessary to the energy-storage battery systems of Development of Novel.
Abundance of the sodium in the earth's crust reaches 2.64%, cheap and similar with the chemical property of lithium.Sodium-ion battery is gathered around
Have that raw material resources are abundant, low in cost, environmental-friendly, energy conversion efficiency is high, have extended cycle life, maintenance cost is low, safety
Many unique advantages such as good will be more and more widely used with the optimization of material property and the maturation of battery technology.
Commercialization secondary cell generally uses volatile, inflammable, explosive organic liquid electrolytes, organic liquid electricity at present
Solution matter easily corrodes positive and negative electrode, will cause battery capacity irreversible loss, while in charge and discharge process, can decompose generation can
Combustion gas body, so as to cause the serious safety problem such as fire and explosion.(such as thermal shock overcharges, is over-discharge, short under abuse state
Road etc.) safety problem is even more serious.
Replace organic liquid electrolytes that can greatly promote battery safety, while solid-state using composite solid electrolyte
Electrolyte can also play the role of diaphragm, can simplify battery structure, reduce cost of manufacture.However existing all-solid sodium ion battery
The key challenge of technology development is that solid electrolyte does not have high ionic conductivity at room temperature, therefore to the electrochemistry of battery
Performance has an impact, and to the exploration of the manufacture craft and overall construction design of all-solid sodium ion battery, there is also not in the industry at present
Foot.
Summary of the invention
It closes and applies the object of the present invention is to provide a kind of Organic-inorganic composite solid electrolyte material and preparation method thereof,
Preparation method through the invention promotes room-temperature conductivity, mechanical performance and the processing performance of solid electrolyte, while simplifying system
Standby step, to promote the industrialized production of solid electrolyte.
To achieve the above object, the present invention provides a kind of preparation method of Organic-inorganic composite solid electrolyte material,
Include:
Polymeric matrix, sodium salt and inorganic electrolyte powder are stocked up according to mass ratio x:(100-x-y): y proportion, and
It is dried in vacuo 4 hours~12 hours at 100 DEG C~200 DEG C respectively；Wherein x>=60, y>=5, and x+y<100；
The inorganic electrolyte powder is added in organic solvent and is dispersed, and in -0.08MPa~-0.1MPa
It is stirred under vacuum 2~4 hours under vacuum degree, obtains the first mixture；
The polymeric matrix is added in first mixture, under -0.08MPa~-0.1MPa vacuum degree
It is stirred under vacuum 0.5~2 hour, is dissolved in the polymeric matrix in first mixture, obtains the second mixture；
The sodium salt is added in second mixture, vacuum is stirred under -0.08MPa~-0.1MPa vacuum degree
It mixes 4~8 hours, obtains solid electrolyte slurry；
The solid electrolyte slurry is poured into mold, solvent is heated at 60 DEG C~80 DEG C and volatilizees completely, then 100
DEG C~120 DEG C at be dried in vacuo 4~12 hours, to obtain Organic-inorganic composite solid electrolyte material.
Preferably, the polymeric matrix includes: Kynoar PVDF, poly- (vinylidene fluoride-co- hexafluoropropene)
One or more of PVDF-HFP and polypropylene carbonate PPC are combined；The sodium salt is sodium perchlorate NaClO4And/or double three
Fluoromethane sulfimide sodium NaTFSI；The inorganic electrolyte powder is NASICON structure, and compound general formula is zNa3La(PO4)2/
Na3-2zZr2-zSi2P1-2zO12-8z, wherein 0 z≤0.5 <；The partial size of inorganic electrolyte powder is 10 μm~100nm.
It is further preferred that the molecular weight of the PVDF and PVDF-HFP is 50,000~120,000；The PPC's
Molecular weight is 50,000~100,000.
Preferably, the organic solvent be N-Methyl pyrrolidone (NMP), n,N-Dimethylformamide (DMF), acetonitrile or
At least one of acetone.
Second aspect, the embodiment of the invention provides what a kind of method according to above-mentioned first aspect was prepared to have
Machine-inorganic compounding solid electrolyte material.
The third aspect, the embodiment of the invention provides a kind of all-solid sodium ion batteries, including described in above-mentioned second aspect
Organic-inorganic composite solid electrolyte material.
Fourth aspect, the embodiment of the invention provides a kind of solid-state Soft Roll sodium-ion batteries, including above-mentioned second aspect institute
The Organic-inorganic composite solid electrolyte material stated.
The preparation method of Organic-inorganic composite solid electrolyte material provided in an embodiment of the present invention, can greatly promote sodium
The safety of ion battery, relative to the preparation of commercial liquid electrolyte, the method for the invention simplifies production stage, reduces life
Cost is produced, there is great application prospect in following sode cell technology and market.Through the invention made from preparation method
Solid electrolyte material has good conductivity at room temperature, mechanical performance and processing performance.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of Organic-inorganic composite solid electrolyte material provided in an embodiment of the present invention；
Fig. 2 is the pictorial diagram of the Organic-inorganic composite solid electrolyte material of one embodiment of the invention preparation；
Fig. 3 is the ac impedance spectroscopy that electrolyte provided in an embodiment of the present invention measures at 25 DEG C of room temperature；
Fig. 4 is the charging and discharging curve figure of solid-state sodium-ion battery provided in an embodiment of the present invention.
Specific embodiment
Below by drawings and examples, technical scheme of the present invention will be described in further detail.
The preparation method of Organic-inorganic composite solid electrolyte material provided in an embodiment of the present invention, main process is such as
Shown in Fig. 1, comprising the following steps:
Step 110, polymeric matrix, sodium salt and inorganic electrolyte powder are matched according to mass ratio x:(100-x-y): y
Than stock, and it is dried in vacuo 4 hours~12 hours at 100 DEG C~200 DEG C respectively；
Wherein, x>=60, y>=5, and x+y<100；
Polymeric matrix include Kynoar (PVDF), poly- (vinylidene fluoride-co- hexafluoropropene) (PVDF-HFP) with
The combination of one or more of polypropylene carbonate (PPC), wherein the molecular weight of PVDF and PVDF-HFP is 50,000~
120,000；The molecular weight of PPC is 50,000~100,000.
Sodium salt is sodium perchlorate (NaClO4) and/or double trifluoromethanesulfonimide sodium (NaTFSI).
Inorganic electrolyte powder is NASICON structure, compound general formula are as follows:
zNa3La(PO4)2/Na3-2zZr2-zSi2P1-2zO12-8z, wherein 0 z≤0.5 <；The partial size of inorganic electrolyte powder is
10 μm~100nm.
Step 120, inorganic electrolyte powder is added in organic solvent and is dispersed, and -0.08MPa~-
It is stirred under vacuum 2~4 hours under the vacuum degree of 0.1MPa, obtains the first mixture；
Wherein, organic solvent be N-Methyl pyrrolidone (NMP), n,N-Dimethylformamide (DMF), in acetonitrile or acetone
At least one.
Step 130, polymeric matrix is added in first mixture, in -0.08MPa~-0.1MPa vacuum
Degree is lower to be stirred under vacuum 0.5~2 hour, is dissolved in polymeric matrix in the first mixture, is obtained the second mixture；
Step 140, sodium salt is added in the second mixture, vacuum is stirred under -0.08MPa~-0.1MPa vacuum degree
It mixes 4~8 hours, obtains solid electrolyte slurry；
Step 150, solid electrolyte slurry is poured into mold, is heated to solvent at 60 DEG C~80 DEG C and volatilizees completely, then
It is dried in vacuo 4~12 hours at 100 DEG C~120 DEG C, to obtain Organic-inorganic composite solid electrolyte material.
The embodiment of the present invention, uses polymer molecular weight for 50,000~1,200,000, and inorganic electrolyte diameter of particle is
10 μm~100nm.Certainly, selected polymer molecular weight and inorganic electrolyte diameter of particle are not particularly limited, only originally
The preferred selection range that embodiment is enumerated.
The present invention uses composite organic-inorganic material, combines inorganic electrolyte mechanical performance and processing performance is good, room temperature
The high advantage of conductivity and organic bath filming performance is good good accessible advantage between electrode, so that advantage is mutual
It mends, thus, it is possible to which the solid electrolyte obtained has good conductivity at room temperature, mechanical performance and processing performance.
By the above method, the preparation to Organic-inorganic composite solid electrolyte material can be completed.Below with some tools
The example of body is illustrated the preparation and its application of Organic-inorganic composite solid electrolyte material respectively.
Embodiment 1
The inorganic electrolyte that partial size is 5 μm is dispersed into stirring 2 hours in NMP.Then, PVDF and NaTFSI is added mixed
Uniform stirring in object is closed, uniform slurry is formed.The solid content of slurry accounts for for 15%, PVDF, 10%, the NaTFSI for accounting for gross mass
The 4% of gross mass, the quality accounting 1% of inorganic electrolyte.By the slurry coating of preparation in grinding tool heat drying, waved to solvent
It distributes complete rear vacuum drying 12 hours, obtains solid electrolyte material.
The material object of the preparation-obtained solid electrolyte material of the present embodiment 1 is as shown in Figure 2.Fig. 3 is the embodiment of the present invention
The ac impedance spectroscopy that is measured at 25 DEG C of room temperature of solid electrolyte material, calculate conductivity is 2 × 10-4S/cm。
Embodiment 2
The inorganic electrolyte that partial size is 200nm is dispersed into stirring 2 hours in NMP.Then, by PVDF, PVDF-HFP with
Uniform stirring in mixture is added in NaTFSI, forms uniform slurry.The solid content of slurry is 12%, and polymeric matrix accounts for total matter
The 8% of amount, wherein the mass ratio of PVDF and PVDF-HFP is 5:5, and NaTFSI accounts for the 3% of gross mass, the quality of inorganic electrolyte
Accounting 2%.By the slurry coating of preparation in grinding tool heat drying, after solvent volatilization completely after be dried in vacuo 12 hours, obtain
Solid electrolyte material.
Embodiment 3
The inorganic electrolyte that partial size is 5 μm is dispersed into stirring 2 hours in DMF.Then, PVDF, PPC and NaTFSI are added
Enter uniform stirring in mixture, forms uniform slurry.The solid content of slurry is 20%, and polymeric matrix accounts for gross mass
15%, wherein the mass ratio of PVDF and PPC is 5:5, and NaTFSI accounts for the 4% of gross mass, the quality accounting 1% of inorganic electrolyte.
By the slurry coating of preparation in grinding tool heat drying, after solvent volatilization completely after be dried in vacuo 12 hours, obtain solid state electrolysis
Material.
Embodiment 4
Using Na [Cu1/3Fe1/3Mn1/3]O2As active substances in cathode materials, by Na [Cu1/3Fe1/3Mn1/3]O2、
NaTFSI, PVDF, Super-P are uniformly mixed according to the ratio of 93:1:3:3, are coated to aluminium collection liquid surface, and 120 DEG C of vacuum are dry
Anode is obtained after dry.Metallic sodium piece is used to be assembled into 2016 buttons as solid electrolyte material obtained in cathode, with embodiment 1
Formula battery.
Button sodium-ion battery is subjected to charge and discharge in 1.5V~4.0V, circulation can be stablized 160 weeks, discharge capacity can for the first time
Up to 110mAh/g.
Embodiment 5
Using Na [Cu1/3Fe1/3Mn1/3]O2As active substances in cathode materials, above-mentioned all solid state electrolyte is as electrolysis
Matter, hard carbon assemble all solid state Soft Roll sodium-ion battery as negative electrode material.Firstly, by Na [Cu1/3Fe1/3Mn1/3]O2、
NaTFSI, PVDF, Super-P are uniformly mixed according to the ratio of 93:1:3:3, are coated to aluminium collection liquid surface and are used as anode, will be hard
Carbon, NaTFSI, LA133 and Super-P are uniformly mixed according to the ratio of 94:1:4:1, are coated to aluminium collection liquid surface as negative
Pole.Molding will be cut after the vacuum drying of positive and negative anodes pole piece, and do tab extraction, by positive plate obtained, negative electrode tab and embodiment 3
The solid electrolyte material of preparation carries out stacking assembling, then successively carries out hot pressing, negative pressure encapsulation, high temperature storage technique, completes
All solid state Soft Roll sodium-ion battery production.
Fig. 4 is charging and discharging curve figure of the solid-state Soft Roll sodium-ion battery of the present embodiment between 1.5V~4.0V, Soft Roll
The design capacity of battery is 700mAh.
The preparation method of Organic-inorganic composite solid electrolyte material provided in an embodiment of the present invention, can greatly promote sodium
The safety of ion battery, relative to the preparation of commercial liquid electrolyte, the method for the invention simplifies production stage, reduces life
Cost is produced, there is great application prospect in following sode cell technology and market.Through the invention made from preparation method
Solid electrolyte material has good conductivity at room temperature, mechanical performance and processing performance.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of Organic-inorganic composite solid electrolyte material, which is characterized in that the preparation method includes:
Polymeric matrix, sodium salt and inorganic electrolyte powder are stocked up according to mass ratio x:(100-x-y): y proportion, and respectively
It is dried in vacuo 4 hours~12 hours at 100 DEG C~200 DEG C；Wherein x>=60, y>=5, and x+y<100；
The inorganic electrolyte powder is added in organic solvent and is dispersed, and in -0.08MPa~-0.1MPa vacuum
Degree is lower to be stirred under vacuum 2~4 hours, and the first mixture is obtained；
The polymeric matrix is added in first mixture, the vacuum under -0.08MPa~-0.1MPa vacuum degree
Stirring 0.5~2 hour, is dissolved in the polymeric matrix in first mixture, obtains the second mixture；
The sodium salt is added in second mixture, under -0.08MPa~-0.1MPa vacuum degree be stirred under vacuum 4~
8 hours, obtain solid electrolyte slurry；
The solid electrolyte slurry is poured into mold, solvent is heated at 60 DEG C~80 DEG C and volatilizees completely, then 100 DEG C~
It is dried in vacuo 4~12 hours at 120 DEG C, to obtain Organic-inorganic composite solid electrolyte material.
2. preparation method according to claim 1, which is characterized in that the polymeric matrix includes: Kynoar
One or more of PVDF, poly- (vinylidene fluoride-co- hexafluoropropene) PVDF-HFP and polypropylene carbonate PPC are combined；Institute
Stating sodium salt is sodium perchlorate NaClO4And/or double trifluoromethanesulfonimide sodium NaTFSI；The inorganic electrolyte powder is
NASICON structure, compound general formula are zNa3La(PO4)2/Na3-2zZr2-zSi2P1-2zO12-8z, wherein 0 z≤0.5 <；Inorganic electrolyte
The partial size of matter powder is 10 μm~100nm.
3. preparation method according to claim 2, which is characterized in that the molecular weight of the PVDF and PVDF-HFP is
50,000~120,000；The molecular weight of the PPC is 50,000~100,000.
4. preparation method according to claim 1, which is characterized in that the organic solvent is N-Methyl pyrrolidone
(NMP), at least one of N,N-dimethylformamide (DMF), acetonitrile or acetone.
5. a kind of Organic-inorganic composite solid state electrolysis material being prepared according to any the method for the claims 1-4
Material.
6. a kind of all-solid sodium ion battery, which is characterized in that the all-solid sodium ion battery includes 5 institute of the claims
The Organic-inorganic composite solid electrolyte material stated.
7. a kind of solid-state Soft Roll sodium-ion battery, which is characterized in that the solid-state Soft Roll sodium-ion battery includes that aforesaid right is wanted
Organic-inorganic composite solid electrolyte material described in asking 5.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110034330A (en) * | 2019-04-10 | 2019-07-19 | 华北电力大学 | A kind of preparation method of lithium/sode cell composite solid electrolyte |
| CN110429329A (en) * | 2019-08-15 | 2019-11-08 | 湖南立方新能源科技有限责任公司 | A kind of preparation method and all-solid sodium ion battery of all-solid sodium ion battery |
| CN111628213A (en) * | 2019-02-28 | 2020-09-04 | 湖南农业大学 | Organic/inorganic composite electrolyte membrane for solid sodium-ion battery and preparation and application thereof |
| CN111987356A (en) * | 2020-08-31 | 2020-11-24 | 上海空间电源研究所 | Long-term circulating sodium-carbon fluoride secondary battery and preparation method thereof |
| CN112909324A (en) * | 2021-01-21 | 2021-06-04 | 北京理工大学 | Inorganic/organic composite solid electrolyte and preparation method and application thereof |
| CN113113661A (en) * | 2021-04-12 | 2021-07-13 | 昆山宝创新能源科技有限公司 | Electrolyte slurry and preparation method and application thereof |
| CN114204110A (en) * | 2021-12-13 | 2022-03-18 | 惠州亿纬锂能股份有限公司 | Composite solid electrolyte, preparation method thereof and lithium ion battery |
| CN117039127A (en) * | 2023-09-11 | 2023-11-10 | 浙江煌能新能源科技有限公司 | Sodium battery composite solid electrolyte, preparation method thereof and sodium battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101002347A (en) * | 2004-09-02 | 2007-07-18 | 株式会社Lg化学 | Organic/inorganic composite porous film and electrochemical device prepared thereby |
| US20160336618A1 (en) * | 2015-05-12 | 2016-11-17 | Samsung Electronics Co., Ltd. | Electrolyte composite and negative electrode and lithium second battery including the electrolyte composite |
| CN107091868A (en) * | 2017-04-26 | 2017-08-25 | 吉林大学 | Electric potential type SO2 sensors and preparation method thereof are blended together by sensitive electrode material of LaxSm1 xFeO3 |
| CN108172898A (en) * | 2018-01-02 | 2018-06-15 | 北京理工大学 | Composite electrolyte and preparation method thereof and all-solid sodium ion battery |
| CN108336398A (en) * | 2018-03-26 | 2018-07-27 | 湘潭大学 | Inorganic/organic polymer composite solid electrolyte film of one kind and preparation method thereof |
-
2018
- 2018-10-23 CN CN201811240261.5A patent/CN109244539A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101002347A (en) * | 2004-09-02 | 2007-07-18 | 株式会社Lg化学 | Organic/inorganic composite porous film and electrochemical device prepared thereby |
| US20160336618A1 (en) * | 2015-05-12 | 2016-11-17 | Samsung Electronics Co., Ltd. | Electrolyte composite and negative electrode and lithium second battery including the electrolyte composite |
| CN107091868A (en) * | 2017-04-26 | 2017-08-25 | 吉林大学 | Electric potential type SO2 sensors and preparation method thereof are blended together by sensitive electrode material of LaxSm1 xFeO3 |
| CN108172898A (en) * | 2018-01-02 | 2018-06-15 | 北京理工大学 | Composite electrolyte and preparation method thereof and all-solid sodium ion battery |
| CN108336398A (en) * | 2018-03-26 | 2018-07-27 | 湘潭大学 | Inorganic/organic polymer composite solid electrolyte film of one kind and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 章志珍: "NASICON结构固态电解质Na3Zr2Si2PO12的制备与改性", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111628213A (en) * | 2019-02-28 | 2020-09-04 | 湖南农业大学 | Organic/inorganic composite electrolyte membrane for solid sodium-ion battery and preparation and application thereof |
| CN110034330A (en) * | 2019-04-10 | 2019-07-19 | 华北电力大学 | A kind of preparation method of lithium/sode cell composite solid electrolyte |
| CN110429329A (en) * | 2019-08-15 | 2019-11-08 | 湖南立方新能源科技有限责任公司 | A kind of preparation method and all-solid sodium ion battery of all-solid sodium ion battery |
| CN111987356A (en) * | 2020-08-31 | 2020-11-24 | 上海空间电源研究所 | Long-term circulating sodium-carbon fluoride secondary battery and preparation method thereof |
| CN112909324A (en) * | 2021-01-21 | 2021-06-04 | 北京理工大学 | Inorganic/organic composite solid electrolyte and preparation method and application thereof |
| CN113113661A (en) * | 2021-04-12 | 2021-07-13 | 昆山宝创新能源科技有限公司 | Electrolyte slurry and preparation method and application thereof |
| CN114204110A (en) * | 2021-12-13 | 2022-03-18 | 惠州亿纬锂能股份有限公司 | Composite solid electrolyte, preparation method thereof and lithium ion battery |
| CN117039127A (en) * | 2023-09-11 | 2023-11-10 | 浙江煌能新能源科技有限公司 | Sodium battery composite solid electrolyte, preparation method thereof and sodium battery |
| CN117039127B (en) * | 2023-09-11 | 2024-02-06 | 浙江煌能新能源科技有限公司 | Sodium battery composite solid electrolyte, preparation method thereof and sodium battery |
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Inventor after: Tian Longfei Inventor after: Zhou Quan Inventor after: Tang Fei Inventor after: Tang Kun Inventor after: Kang Libin Inventor after: Qi Xingguo Inventor after: Hu Yongsheng Inventor before: Tian Longfei Inventor before: Zhou Quan Inventor before: Tang Fei Inventor before: Tang Kun Inventor before: Kang Libin Inventor before: Qi Xingguo |
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Application publication date: 20190118 |