CN109096433B - Single-ion conductor polymer lithium salt and preparation method thereof - Google Patents
Single-ion conductor polymer lithium salt and preparation method thereof Download PDFInfo
- Publication number
- CN109096433B CN109096433B CN201710472018.5A CN201710472018A CN109096433B CN 109096433 B CN109096433 B CN 109096433B CN 201710472018 A CN201710472018 A CN 201710472018A CN 109096433 B CN109096433 B CN 109096433B
- Authority
- CN
- China
- Prior art keywords
- lithium salt
- lithium
- maleic anhydride
- polymer
- styryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a single-ion conductor polymer lithium salt and a preparation method thereof. Firstly, generating styryl bissulfonylimide from p-styrene sulfonyl chloride and benzene sulfonamide under the action of triethylamine and 4-dimethylamino pyridine, and neutralizing with lithium hydroxide to obtain styryl bissulfonylimide lithium salt monomer. Taking azobisisobutyronitrile as an initiator, bonding the lithium styryl bissulfonylimide and the maleic anhydride together by a simple free radical copolymerization mode to form the vinyl benzenesulfonylimide lithium salt and maleic anhydride alternating polymer. The invention introduces the unit with high dielectric constant, maleic anhydride, into the existing polymer lithium salt skeleton or chain segment, and promotes the dissociation of lithium ions through the interaction between the unit and the lithium ions, thereby being a way for effectively increasing the concentration of free lithium ions and improving the conductivity and the transference number of the lithium ions at room temperature.
Description
Technical Field
The invention relates to preparation of a novel lithium single-ion polymer lithium salt, in particular to preparation of a bis-benzenesulfonylimine lithium-based single-ion polymer lithium salt with an alternating structure and application of the lithium-based single-ion polymer lithium salt in a polymer electrolyte.
Background
Compared with the traditional liquid electrolyte lithium secondary battery, the organic polymer electrolyte-based all-solid-state lithium battery has larger promotion space in the aspects of battery energy density, working temperature interval, cycle life and the like, and is an important development direction of the lithium secondary battery. The organic all-solid-state polymer electrolyte system not only has the advantages of light weight, good viscoelasticity, easy film formation, wide electrochemical window, good chemical stability and the like, but also can well inhibit the dendritic crystal problem of the lithium metal battery. The lithium battery using the organic all-solid-state polymer electrolyte can overcome the problems of easy liquid leakage, short circuit, insufficient safety and the like of a liquid electrolyte battery, and simultaneously overcomes the defects of large brittleness, poor film forming property and poor mechanical deformation of an inorganic solid electrolyte. In addition, the battery can also adopt flexible packaging materials, such as aluminum plastic films and the like, so that the battery is allowed to bend and fold, the appearance design of the battery can be more flexible and convenient, the total weight is light, and the mass specific energy is greatly improved.
Generally, organic solid polymer electrolytes are conductive to both anions and cations, the transference number of lithium ions is low, only between 0.2 and 0.5, and some lithium ions are even less than 0.1, so that the application of the polymer electrolytes is greatly limited. Since most electrochemical devices involve dc polarization, during charging and discharging, anions will concentrate at the electrode/electrolyte interface, causing concentration polarization phenomenon, generating a polarization voltage opposite to the applied electric field, and as a result, hindering the migration of lithium ions, reducing the stability of the battery charging and discharging current, and reducing the energy efficiency and service life of the battery. An effective way to solve the problem of internal polarization of organic solid polymer electrolytes is to prepare polymer electrolytes with lithium ion transport numbers close to 1, and the most important of them is to prepare single-ion polymer lithium salts with high lithium ion transport numbers. The biggest limiting factors of the current lithium battery based on single-ion polymer lithium salt polymer electrolyte are low ionic conductivity and lithium ion transference number under the room temperature condition. Therefore, how to effectively improve the ionic conductivity and lithium ion transport number of the organic solid polymer electrolyte at room temperature has been the hot point of research.
Disclosure of Invention
The invention designs a novel single-ion polymer lithium salt with an alternative structure and provides a preparation method thereof, aiming at the problem of lower ionic conductivity and lithium ion transference number under the room temperature condition.
The technical purpose of the invention is realized by adopting the following technical scheme:
the single-ion conductor polymer lithium salt is formed by copolymerizing styryl bis-sulfonyl imide lithium salt (STSSSILi) and Maleic Anhydride (MA), and the structure of the single-ion conductor polymer lithium salt is shown as the formula (I)
Wherein n represents the degree of polymerization, the maleic anhydride is chosen in excess when the copolymerization is carried out so that the copolymerization of the styrene-based derivative with maleic anhydride tends to alternate polymerization, the molar ratio of styrene-based bis-sulfonylimide lithium salt (STSSSIL) to Maleic Anhydride (MA) being 1: (1-1.5), preferably 1: (1.05-1.2).
The degree of polymerization n is at least 100, preferably from 200 to 1000, or from 500 to 800.
A process for preparing the lithium salt of single-ion conducting polymer includes such steps as uniformly dispersing the lithium salt of styryl bissulfonylimide and maleic anhydride in dimethyl sulfoxide (DMSO), adding thermal trigger, discharging oxygen, heating to the temp higher than the trigger for polymerizing reaction, introducing air to stop the reaction, depositing the solution of polymer in tetrahydrofuran, and depositing three times to remove unreacted monomer.
Further, the maleic anhydride excess is selected in carrying out the copolymerization so that the copolymerization of the styrene-based derivative with maleic anhydride tends to alternate polymerization, and the molar ratio of styrene-based bissulfonylimide lithium salt (stsil) to Maleic Anhydride (MA) is 1: (1-1.5), preferably 1: (1.05-1.2).
Furthermore, the thermal initiator is Azobisisobutyronitrile (AIBN), or Benzoyl Peroxide (BPO), and the initiation temperature is 60-80 ℃.
The ratio of the amount of the substance of the thermal initiator to the sum of the amounts of the substances of the two monomers is 0.1 to 0.5% (i.e., a molar ratio), preferably 0.1 to 0.3%.
Furthermore, the free radical polymerization of the monomer lithium styryl bissulfonylimide salt with maleic anhydride is initiated using a thermal initiator, the maleic anhydride being chosen in excess so that the copolymerization of the styryl derivative with maleic anhydride tends to alternate, as shown in FIG. 5, the peak at 136.6 in the carbon spectrum evidences its alternating structure, with a polymerization time of at least 20 hours, to allow sufficient polymerization of the added monomer, preferably 24-48 hours.
Furthermore, the structure and preparation route of the lithium styryl bissulfonylimide salt (STSSILI) are shown as the following chemical formula:
uniformly dispersing benzene sulfonamide in acetonitrile, adding triethylamine and 4-dimethylaminopyridine, uniformly dispersing, and placing in an ice bath at 0 ℃, wherein the molar ratio of the triethylamine to the benzene sulfonamide is (1-3): the molar ratio of the 1, 4-dimethylamino pyridine to the benzene sulfonamide is (1-2): 1; uniformly dispersing p-styrene sulfonyl chloride with the molar ratio equal to that of benzene sulfonamide in acetonitrile, dropwise adding the solution into acetonitrile solution of benzene sulfonamide, standing the solution after dropwise adding, heating the solution to room temperature of 20-25 ℃ for reaction to obtain styryl bis-sulfonyl imide, then placing the styryl bis-sulfonyl imide and lithium hydroxide with the molar ratio equal to that of the benzene sulfonamide in distilled water, stirring the solution to obtain transparent solution, and spin-drying the distilled water by using a rotary evaporator to obtain styryl bis-sulfonyl imide lithium salt monomer (STSI).
Specifically, the benzene sulfonamide is dissolved in an acetonitrile solution to prepare a solution with the concentration of 0.5-1 mol/L. Triethylamine (Et)3N) and 4-Dimethylaminopyridine (DMAP) were added to an acetonitrile solution of benzenesulfonamide in an amount of 3 times and 1 time, respectively, based on the molar amount of benzenesulfonamide, and placed in an ice bath at 0 ℃ for 30 minutes. An equal volume of acetonitrile solution of p-styrenesulfonyl chloride was prepared according to the concentration of the above-mentioned benzenesulfonamide acetonitrile solution, and slowly added dropwise to the benzenesulfonamide acetonitrile solution. After the completion of the dropwise addition, the mixture was allowed to stand for 30 minutes, warmed to room temperature and reacted for 48 hours. After the reaction was completed, acetonitrile in the system was removed by a rotary evaporator, and the obtained solid was redissolved in methylene chloride. A4% excess of saturated sodium bicarbonate (NaHCO) was then used3) The solution was washed with an aqueous solution and 1mol/L hydrochloric acid. After washing, methylene chloride was again spin-dried using a rotary evaporator to obtain styryl bissulfonylimide. Equivalent molar amounts of styryl bis-sulfonyl imide and lithium hydroxide (LiOH) were put in 50ml of distilled water and stirred to a transparent solution, and then the distilled water was spin-dried using a rotary evaporator to obtain styryl bis-sulfonyl imide lithium salt monomer (stsisii).
Through nuclear magnetic resonance and infrared spectrum tests, the styrene-based bis-sulfonyl imide lithium salt monomer (STSSILI) is judged to be successfully prepared, and the single-ion conductor polymer lithium salt shows an alternate copolymerization structure of the styrene-based bis-sulfonyl imide lithium salt monomer and maleic anhydride.
The invention introduces a unit with high dielectric constant of maleic anhydride into the existing polymer lithium salt skeleton or chain segment, and promotes the dissociation of lithium ions through the interaction between the unit and the lithium ions, which is a way to effectively increase the concentration of free lithium ions and improve the conductivity and the migration number of the lithium ions at room temperature, namely the application of the single-ion conductor polymer lithium salt in improving the conductivity and the migration number of the lithium ions at room temperature (20-25 ℃).
Drawings
FIG. 1 is a Fourier infrared absorption spectrum of a styryl bis (sulfonyl) imide lithium salt monomer (STSSILI) synthesized in the present invention.
FIG. 2 shows nuclear magnetic hydrogen spectrum of styryl bis (sulfonyl) imide lithium salt monomer (STSSSILi) synthesized in the present invention.
FIG. 3 is a Fourier infrared absorption spectrum of a single ion conductive polymer lithium salt P (STSSSILi-alt-MA) synthesized in the present invention.
FIG. 4 is a nuclear magnetic hydrogen spectrum of single ion conductive polymer lithium salt P (STSSSILi-alt-MA) synthesized in the present invention.
FIG. 5 shows the nuclear magnetic carbon spectrum of the single ion conductive polymer lithium salt P (STSSSILi-alt-MA) synthesized in the present invention.
FIG. 6 is a graph showing the room temperature AC impedance of a polymer electrolyte made of lithium salt P (STSSILI-alt-MA), a single ion conductor polymer synthesized in the present invention.
FIG. 7 is a graph showing the current polarization curve of a polymer electrolyte made of lithium salt of single ion conductor polymer P (STSSSILi-alt-MA) synthesized in the present invention.
FIG. 8 is a graph showing the AC impedance before and after polarization of a polymer electrolyte made of lithium salt P (STSSILI-alt-MA), a single ion conductor polymer synthesized in the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
Firstly, the preparation of styryl bissulfonylimide lithium salt monomer (STSSII) is carried out
Dissolving benzene sulfonamide in acetonitrile solution to prepare solution with the concentration of 0.5 mol/L. Triethylamine (Et)3N) and 4-Dimethylaminopyridine (DMAP) were added to an acetonitrile solution of benzenesulfonamide in an amount of 3 times and 1 time, respectively, based on the molar amount of benzenesulfonamide, and the mixture was left at 0 ℃ to separateWas cooled in an ice bath for 30 minutes. An equal volume of acetonitrile solution of p-styrenesulfonyl chloride was prepared according to the concentration of the above-mentioned benzenesulfonamide acetonitrile solution, and slowly added dropwise to the benzenesulfonamide acetonitrile solution. After the completion of the dropwise addition, the mixture was allowed to stand for 30 minutes, warmed to room temperature and reacted for 48 hours. After the reaction was completed, acetonitrile in the system was removed by a rotary evaporator, and the obtained solid was redissolved in methylene chloride. A4% excess by weight of saturated sodium bicarbonate (NaHCO) was used in succession3) The solution was washed with 1mol/L hydrochloric acid (aqueous solution of hydrogen chloride). After washing, methylene chloride was again spin-dried using a rotary evaporator to obtain styryl bissulfonylimide. Equivalent molar amounts of styryl bis-sulfonyl imide and lithium hydroxide (LiOH) were put in 50ml of distilled water and stirred to a transparent solution, and then the distilled water was spin-dried using a rotary evaporator to obtain styryl bis-sulfonyl imide lithium salt monomer (stsisii).
EXAMPLE 1 preparation of lithium styryl bis-sulfonylimide salt and maleic anhydride alternating Polymer P (STSSILI-alt-MA)
Lithium salt monomer STSSSILi and Maleic Anhydride (MA) are mixed according to a molar ratio of 1: 1.2 into a polymerization tube, adding dimethyl sulfoxide (DMSO) for dissolution, and adding 0.1% (by mol) Azobisisobutyronitrile (AIBN). The polymerization tube is put into liquid nitrogen for cold shortage, nitrogen gas is introduced and vacuum pumping is carried out for three times, then the tube is sealed by an alcohol blast burner and put into an oil bath kettle at 60 ℃ for reaction for 48 hours. After the reaction was completed, the polymerization tube was opened to expose the tube to air. The polymer in DMSO was precipitated into tetrahydrofuran three times to remove unreacted monomer.
EXAMPLE 2 preparation of lithium styryl bis-sulfonylimide salt and maleic anhydride alternating Polymer P (STSSILI-alt-MA)
Lithium salt monomer STSSSILi and Maleic Anhydride (MA) are mixed according to a molar ratio of 1: 1.05 into a polymerization tube, dimethyl sulfoxide (DMSO) was added to dissolve, and 0.2% (molar ratio) of Azobisisobutyronitrile (AIBN) was added. Putting the polymerization tube into liquid nitrogen for cold cutting, introducing nitrogen gas, vacuumizing for three times, sealing the tube by using an alcohol blast burner, and putting the tube into an oil bath kettle at the temperature of 80 ℃ for reaction for 36 hours. After the reaction was completed, the polymerization tube was opened to expose the tube to air. The polymer in DMSO was precipitated into tetrahydrofuran three times to remove unreacted monomer.
Example 3-preparation of styrene-based bis-sulfonylimide lithium salt alternating polymer with maleic anhydride P (ststiii-alt-MA) lithium salt monomer ststii was mixed with Maleic Anhydride (MA) in a molar ratio of 1: 1.2 into a polymerization tube, adding dimethyl sulfoxide (DMSO) for dissolution, and adding 0.3% (molar ratio) Azobisisobutyronitrile (AIBN). Putting the polymerization tube into liquid nitrogen for cold cutting, introducing nitrogen gas, vacuumizing for three times, sealing the tube by using an alcohol blast burner, and putting the tube into an oil bath kettle at the temperature of 70 ℃ for reaction for 40 hours. After the reaction was completed, the polymerization tube was opened to expose the tube to air. The polymer in DMSO was precipitated into tetrahydrofuran three times to remove unreacted monomer.
EXAMPLE 4 preparation of lithium styryl bis-sulfonylimide salt and maleic anhydride alternating Polymer P (STSSILI-alt-MA)
Lithium salt monomer STSSSILi and Maleic Anhydride (MA) are mixed according to a molar ratio of 1: 1.3 into a polymerization tube, adding dimethyl sulfoxide (DMSO) for dissolution, and adding 0.5% (molar ratio) Azobisisobutyronitrile (AIBN). The polymerization tube is put into liquid nitrogen for cold shortage, nitrogen gas is introduced and vacuum pumping is carried out for three times, then the tube is sealed by an alcohol blast burner and put into an oil bath kettle at 60 ℃ for reaction for 48 hours. After the reaction was completed, the polymerization tube was opened to expose the tube to air. The polymer in DMSO was precipitated into tetrahydrofuran three times to remove unreacted monomer.
The alternating polymer P (STSSSILi-alt-MA) of the above embodiment of the present invention is used as a polymer electrolyte, stainless steel sheets are used as the anode and cathode, a room temperature AC impedance test is performed by using an electrochemical workstation of Shanghai Chenghua company, and the room temperature AC impedance test is fitted and calculated to obtain a room temperature conductivity average of 2.5-2.8 mS cm-1(ii) a And replacing the stainless steel sheet with a lithium sheet, carrying out a current polarization test, wherein a typical room-temperature alternating current impedance diagram, a current polarization curve and alternating current impedance diagrams before and after polarization are shown in the figure, and calculating the average migration number to be more than 0.98.
The preparation of alternating polymer P (STSSILI-alt-MA) was achieved by adjusting the preparation process parameters according to the present disclosure, and the performance as a polymer electrolyte was substantially the same as the above examples. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (9)
1. The single-ion conductor polymer lithium salt is characterized by being formed by copolymerizing styryl bissulfonyl imide lithium salt and maleic anhydride, and the structure of the single-ion conductor polymer lithium salt is shown as the formula (I)
Wherein n represents the degree of polymerization, and the maleic anhydride is selected in excess when the copolymerization is carried out so that the copolymerization of the styrene-based derivative with the maleic anhydride tends to alternate polymerization, the molar ratio of the styrene-based bissulfonylimide lithium salt to the maleic anhydride being 1: (1.05-1.2) and the degree of polymerization n is 200-1000.
2. The lithium salt of a single-ion conductive polymer of claim 1, wherein the degree of polymerization n is from 500 to 800.
3. The method of claim 1, wherein the lithium salt of a mono-ionic conducting polymer is prepared by uniformly dispersing a lithium salt of styryl bis-sulfonylimide and maleic anhydride in dimethyl sulfoxide as a solvent, adding a thermal initiator and discharging oxygen, and then heating to a temperature higher than the initiation temperature to perform polymerization.
4. The method of claim 3, wherein the reaction is terminated by introducing air, and the polymer solution of dimethylsulfoxide is precipitated in tetrahydrofuran three times to remove unreacted monomers.
5. The method of claim 3, wherein the thermal initiator is azobisisobutyronitrile or benzoyl peroxide, and the initiation temperature is 60-80 ℃.
6. The method of claim 3, wherein the ratio of the amount of the thermal initiator to the sum of the amounts of the two monomers is 0.1 to 0.5%.
7. The method of claim 3, wherein the polymerization time is at least 20 hours to allow sufficient polymerization of the additional monomer.
8. The method of claim 3, wherein the lithium salt of styryl bis-sulfonimide is prepared by the following steps: uniformly dispersing benzene sulfonamide in acetonitrile, adding triethylamine and 4-dimethylaminopyridine, uniformly dispersing, and placing in an ice bath at 0 ℃, wherein the molar ratio of the triethylamine to the benzene sulfonamide is (1-3): the molar ratio of the 1, 4-dimethylamino pyridine to the benzene sulfonamide is (1-2): 1; uniformly dispersing p-styrene sulfonyl chloride with the molar ratio equal to that of benzene sulfonamide in acetonitrile, dropwise adding the solution into acetonitrile solution of benzene sulfonamide, standing the solution after dropwise adding, heating the solution to room temperature of 20-25 ℃ for reaction to obtain styryl bis-sulfonyl imide, then placing the styryl bis-sulfonyl imide and lithium hydroxide with the molar ratio equal to that of the benzene sulfonamide in distilled water, stirring the solution to obtain transparent solution, and spin-drying the distilled water by using a rotary evaporator to obtain the styryl bis-sulfonyl imide lithium salt monomer.
9. Use of a single-ion conducting polymer lithium salt according to claim 1 or 2 for increasing the lithium ion conductivity and transport number at room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710472018.5A CN109096433B (en) | 2017-06-20 | 2017-06-20 | Single-ion conductor polymer lithium salt and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710472018.5A CN109096433B (en) | 2017-06-20 | 2017-06-20 | Single-ion conductor polymer lithium salt and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109096433A CN109096433A (en) | 2018-12-28 |
| CN109096433B true CN109096433B (en) | 2020-08-21 |
Family
ID=64796026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710472018.5A Active CN109096433B (en) | 2017-06-20 | 2017-06-20 | Single-ion conductor polymer lithium salt and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109096433B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552450A (en) * | 2019-09-10 | 2021-03-26 | 天津大学 | Single-ion alternating copolymer lithium salt and preparation method thereof |
| EP3832757A1 (en) * | 2019-12-03 | 2021-06-09 | Belenos Clean Power Holding AG | Single-ion conductive polymers for electrochemical devices |
| CN112018439A (en) * | 2020-08-31 | 2020-12-01 | 天津大学 | Preparation and application of solid electrolyte based on polyvinyl benzene sulfonic acid lithium-citric acid carbon dots |
| CN112133962A (en) * | 2020-09-25 | 2020-12-25 | 天津大学 | Preparation method of bis (trifluoromethyl) sulfimide lithium-glucose carbon quantum dot solid electrolyte |
| GB202015436D0 (en) * | 2020-09-30 | 2020-11-11 | Fujifilm Mfg Europe Bv | Compositions and polymer films |
| CN113097566B (en) * | 2021-04-01 | 2022-04-05 | 山东海科新源材料科技股份有限公司 | Imide additive containing sulfonated side chain, electrolyte and lithium ion battery thereof |
| CN116554384B (en) * | 2023-07-12 | 2023-09-22 | 深圳海辰储能控制技术有限公司 | Modified polyvinylidene fluoride, preparation method thereof, active material composition, positive electrode plate and energy storage device |
| CN116554804B (en) * | 2023-07-12 | 2023-09-26 | 深圳海辰储能控制技术有限公司 | Modified styrene-butadiene latex binder, preparation method thereof, battery pole piece and secondary battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816096B (en) * | 2011-06-10 | 2014-09-24 | 华中科技大学 | Imine alkali metal salt and ion liquid and application of same as non water electrolyte |
| CN103509153B (en) * | 2012-06-15 | 2016-05-25 | 华中科技大学 | A kind of polymer list ionic electrolytes and preparation method thereof |
| KR102411660B1 (en) * | 2015-05-06 | 2022-06-21 | 삼성전자주식회사 | Negative electrode for lithium battery and lithium battery comprising the same |
| CN106674391A (en) * | 2015-11-10 | 2017-05-17 | 华中科技大学 | Iamine-polyanion lithium salt and preparation method thereof as well as application of iamine-polyanion lithium salt as nonaqueous electrolyte |
-
2017
- 2017-06-20 CN CN201710472018.5A patent/CN109096433B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109096433A (en) | 2018-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109096433B (en) | Single-ion conductor polymer lithium salt and preparation method thereof | |
| CN106935904B (en) | A kind of lithium single-ion conductor polymer dielectric based on functionalization lithium borate salt | |
| Yin et al. | An imidazolium-based polymerized ionic liquid via novel synthetic strategy as polymer electrolytes for lithium ion batteries | |
| CN107919496B (en) | Method for preparing single-ion solid polymer electrolyte | |
| CN103509153B (en) | A kind of polymer list ionic electrolytes and preparation method thereof | |
| CN107579277B (en) | Three arm branched polymeric ionic liquid gel electrolyte and preparation method thereof | |
| Wang et al. | Low-temperature and high-rate Zn metal batteries enabled by mitigating Zn2+ concentration polarization | |
| CN109776709B (en) | Poly (p-styrenesulfonyl) (trifluoromethyl sulfonyl) imide lithium-poly (ethylene carbonate) copolymer and application thereof | |
| CN104031193A (en) | Polymer ion liquid electrolyte and preparation method thereof | |
| CN110233288A (en) | Full solid state polymer electrolyte and preparation method thereof with half interpenetrating network structure | |
| CN107256981B (en) | A kind of preparation method of eight arms liquid crystalline block copolymers composite electrolyte | |
| CN111668539B (en) | PVA/Li + Preparation method of/PEO interpenetrating network structure composite gel electrolyte | |
| CN103633367A (en) | Gel polymer electrolyte, polymer lithium ion battery and making method of polymer lithium ion battery | |
| CN102403533B (en) | Gel-state polymer electrolyte of lithium-ion battery and preparation method | |
| CN111554974A (en) | Preparation method of polyethylene glycol diacrylate-based gel electrolyte | |
| CN103165936B (en) | Solid electrolyte and use the lithium-base battery of this solid electrolyte | |
| CN111786018B (en) | High-voltage polymer electrolyte, high-voltage polymer lithium metal battery and preparation method of battery | |
| CN106684443A (en) | Preparation method for modified graphene oxide-doped solid polymer electrolyte | |
| CN108341933A (en) | A kind of single-ion polymer electrolyte, single-ion polymer electrolyte complex film and preparation method thereof, lithium ion battery | |
| CN115505115B (en) | Composition for preparing gel electrolyte, electrolyte and battery thereof | |
| CN111525187B (en) | Sulfonated polyvinyl alcohol solid polymer electrolyte membrane for lithium battery and preparation method thereof | |
| CN113270641A (en) | Preparation method of single-ion conductor gel electrolyte based on in-situ polymerization | |
| CN112481829A (en) | Single-ion conductor polymer electrolyte composite diaphragm, and preparation method and application thereof | |
| Ren et al. | Hydroxypropylmethylcellulose: Functional material carrier for in-situ solid electrolyte engineering of advanced lithium metal batteries | |
| CN112552450A (en) | Single-ion alternating copolymer lithium salt and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |