CN105218992A - Sulfonated graphene metal-salt solid polymer electrolyte and its preparation method and application - Google Patents
Sulfonated graphene metal-salt solid polymer electrolyte and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of sulfonated graphene metal-salt solid polymer electrolyte and its preparation method and application.This sulfonated graphene metal-salt solid polymer electrolyte comprises sulfonated graphene metal-salt and solid polymer electrolyte, and this sulfonated graphene metal-salt reacts obtained by the part sulfonic acid metallizing thing in sulfonated graphene; This solid polymer electrolyte is selected from poly-hydroxy base polymer; Obtained by part hydroxyl reaction in the part sulfonic acid in sulfonated graphene and solid polymer electrolyte between sulfonated graphene metal-salt and solid polymer electrolyte.Sulfonated graphene metal-salt solid polymer electrolyte of the present invention has comparatively high ionic conductivity; wider electrochemical window; with the chemistry of electrode materials and electrochemistry consistency good; in the electrochemistry such as lithium ion battery, ultracapacitor/physics energy storage device, there is wide application prospect; and preparation technology is simple, easy to implement and regulation and control, reaction conditions is gentle; raw material sources are extensive, are convenient to large-scale production.
Description
Technical field
The present invention relates to a kind of solid state electrolyte, particularly a kind of sulfonated graphene metal-salt solid polymer electrolyte, its preparation method and application, such as, application in the electrochemistry such as electrical condenser, battery and/or physics energy storage device.
Background technology
For a long time, ionogen has important application as the supplier of the ion that can transmit or the passage of ion transport in fields such as secondary cell, electrical condenser, sensor and dye sensitization solar batterys.Traditional electrolyte matter is liquid electrolyte system mainly, although it has ionic conductivity advantages of higher, but there is easy-to-leak liquid, the shortcoming such as inflammable and explosive simultaneously.For this reason, people have developed again the ionogen of various new, and wherein a kind of what have application prospect is all solid state electrolyte.Particularly in recent years, rapidly, the composition of this based solid electrolyte existing mixes an alkali metal salt in polymkeric substance in the solid electrolyte development of polymeric matrix.Common polymeric matrix comprises polyoxyethylene (PEO), polyacrylonitrile (PAN) etc., conventional basic metal is lithium salts, negatively charged ion has impact to electroconductibility, and in matrix, contained solvent molecule (as carbonic ether) also has a significant impact material property simultaneously.In addition, the problem that existing polymer dielectric ubiquity ionic conductivity is low, lithium ion transference number is little and electrochemical stability is poor.
In order to improve the performances such as the ionic conductivity of solid polymer electrolyte, researchist has developed interpolation solid inorganic filler and has formed the technology of composite electrolyte, research shows, compared with not filled, the specific conductivity of composite polymer electrolyte, mechanical property, all obtain certain improvement with the interface stability etc. of electrode.But inorganic nano-filler exists in polymeric matrix easily reunites, disperses the problems such as uneven, limits the further raising of composite polymer electrolyte electrical property.
Such as, the filler as solid polymer electrolyte such as Graphene, graphene oxide is have employed among some researchs, the high ionic conductivity (about 2.1S/cm) had to utilizing grapheme material improves the ionic conductivity of polymeric matrix, but it cannot overcome grapheme material equally and the problem such as to reunite in polymeric matrix.Although the documents such as such as CN103881278A, CN102585280A, CN103560268A, CN102891335A propose, the scheme of its agglomeration is improved by carrying out surface modification to grapheme material, but these technology ubiquity processes are complicated, high in cost of production defect, and in obtained product, in fact still there is the problem of certain Graphene reunion, make its performance, particularly to promote amplitude still very limited for ionic conductivity, electrochemical window width etc., and with the chemistry of common electrodes material and electrochemistry consistency also still to be improved.
Summary of the invention
In view of deficiency of the prior art, the object of the invention is to mainly provide a kind of sulfonated graphene metal-salt solid polymer electrolyte and preparation method thereof.
For realizing aforementioned invention object, the technical solution used in the present invention comprises:
A kind of sulfonated graphene metal-salt solid polymer electrolyte is provided among some case study on implementation, it is formed primarily of the solid polymer electrolyte containing sulfonic sulfonated graphene metal-salt and hydroxyl reacts to each other, and described sulfonated graphene metal-salt is formed primarily of sulfonated graphene metallizing thing reacts to each other.
Particularly, described sulfonated graphene metal-salt solid polymer electrolyte comprise containing sulfonic sulfonated graphene metal-salt and with the solid polymer electrolyte of described sulfonated graphene metal-salt by the hydroxyl of covalent bonds, wherein said sulfonated graphene metal-salt primarily of sulfonated graphene and by ionic linkage be incorporated into sulfonated graphene surface metallic compound composition.
Further, described sulfonated graphene metal-salt solid polymer electrolyte to be combined with each other by part sulfonic group and at least part of hydroxyl reaction primarily of the solid polymer electrolyte containing sulfonic sulfonated graphene metal-salt and hydroxyl and is formed.
Further, described sulfonated graphene metal-salt is formed primarily of the part sulfonic group in metallic compound and sulfonated graphene reacts.
Among some case study on implementation, additionally provide a kind of preparation method of sulfonated graphene metal-salt solid polymer electrolyte, it comprises:
S1, sulfonated graphene is dispersed in organic solvent, forms sulfonated graphene solution;
S2, in described sulfonated graphene solution, add metallic compound in an inert atmosphere, and at room temperature more than stirring reaction 1h, be preferably 1h ~ 6h, obtain sulfonated graphene metal salt solution;
S3, in described sulfonated graphene metal salt solution, add solid polymer electrolyte, and preferably at 40 DEG C ~ 85 DEG C more than stirring reaction 1h, be especially preferably 1h ~ 24h, obtain sulfonated graphene metal-salt solid polymer electrolyte solution;
S4, drying treatment is carried out to described sulfonated graphene metal-salt solid polymer electrolyte solution, obtain described sulfonated graphene metal-salt solid polymer electrolyte.
Among some comparatively preferred case study on implementation, the concentration of described sulfonated graphene solution is 0.1500g/L ~ 500g/L.
Among some comparatively preferred case study on implementation, step S4 comprises: by described sulfonated graphene metal-salt solid polymer electrolyte solution 85 DEG C ~ 200 DEG C oven dry, obtain described sulfonated graphene metal-salt solid polymer electrolyte.
Wherein, described organic solvent can be selected from but be not limited to dimethyl sulfoxide (DMSO) (DMSO), dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAC), ethyl cellulose (EC), polycarbonate (be called for short PC), any one or two or more combinations in Methyl ethyl carbonate (EMC).
Wherein, described metallic compound can preferably from but be not limited to Lithium Oxide 98min and/or lithium hydroxide, sodium oxide and/or sodium hydroxide, potassium oxide and/or potassium hydroxide, magnesium oxide and/or magnesium hydroxide, calcium oxide and/or calcium hydroxide, aluminum oxide and/or aluminium hydroxide.
Among some comparatively preferred case study on implementation, the addition of metallic compound described in step S2 in sulfonated graphene solution is 0.3g/L ~ 30g/L.
Among some comparatively preferred case study on implementation, the radial dimension of described sulfonated graphene is 0.05 μm ~ 100 μm, and thickness is 0.5nm ~ 20nm, and wherein sulfonic content is expressed as 12:1 ~ 3:1 with the mol ratio of carbon sulphur.
It should be noted that, sulfonated graphene of the present invention can by the scheme self-control known to commercially available approach or industry.
Among some comparatively preferred case study on implementation, in described sulfonated graphene, in sulfonate radical and described metallic compound, the mol ratio of metallic element is 1:1 ~ 5:1.
Wherein, described solid polymer electrolyte is at least selected from poly-hydroxy base polymer, such as can preferably from but be not limited to polyvinyl alcohol, polyoxyethylene glycol, polyglycerol, polyvinylpyrrolidone, Mierocrystalline cellulose, chitosan, cyclodextrin, any one or two or more combinations in phytic acid.
Among some comparatively preferred case study on implementation, the addition of solid polymer electrolyte described in step S3 in sulfonated graphene metal salt solution is 1g/L ~ 100g/L.
Among some comparatively preferred case study on implementation, in described sulfonated graphene, in sulfonate radical and described solid polymer electrolyte, the mol ratio of hydroxyl is 5:1 ~ 25:1.
Present invention also offers the sulfonated graphene metal-salt solid polymer electrolyte prepared by any one method aforementioned.
Further, the ionic conductivity of described sulfonated graphene metal-salt solid polymer electrolyte is 10
-2the S/cm order of magnitude, electrochemical window scope is 5.4V ~ 6.2V.
Present invention also offers the purposes of described sulfonated graphene metal-salt solid polymer electrolyte, such as, application in preparation electrochemistry and/or physics energy storage device.
Among some embodiments, provide a kind of electrochemistry and/or physics energy storage device, it comprises aforesaid sulfonated graphene metal-salt solid polymer electrolyte.
Further, described electrochemistry/physics energy storage device includes but not limited to electrical condenser or battery, such as, described electrical condenser comprises electrolytic condenser, ultracapacitor or hybrid super capacitor, such as, described battery lithium ion battery, sodium-ion battery, kalium ion battery, Magnesium ion battery, calcium ion battery, aluminum ion battery, fuel cell or fuel sensitization solar battery.
Among some embodiments, provide a kind of lithium ion battery, it comprises positive and negative plate, is placed in the barrier film between positive plate and negative plate and aforesaid sulfonated graphene lithium salts solid polymer electrolyte.
Among some embodiments, provide a kind of sodium-ion battery, it comprises positive and negative plate, is placed in the barrier film between positive plate and negative plate and aforesaid sulfonated graphene sodium salt solid polymer electrolyte.
Among some embodiments, provide a kind of kalium ion battery, it comprises positive and negative plate, is placed in the barrier film between positive plate and negative plate and aforesaid sulfonated graphene sylvite solid polymer electrolyte.
Among some embodiments, provide a kind of Magnesium ion battery, it comprises positive and negative plate, is placed in the barrier film between positive plate and negative plate and aforesaid sulfonated graphene magnesium salts solid polymer electrolyte.
Among some embodiments, provide a kind of calcium ion battery, it comprises positive and negative plate, is placed in the barrier film between positive plate and negative plate and aforesaid sulfonated graphene calcium salt solid polymer electrolyte.
Among some embodiments, provide a kind of aluminum ion battery, it comprises positive and negative plate, is placed in the barrier film between positive plate and negative plate and aforesaid sulfonated graphene aluminium salt solid polymer electrolyte.
Compared with prior art, the present invention at least tool have the following advantages:
(1) sulfonated graphene metal-salt solid polymer electrolyte of the present invention has higher ionic conductivity, wider electrochemical window, with the chemistry of electrode materials and electrochemistry consistency good, in the electrochemical storage device such as lithium ion battery, ultracapacitor, there is wide application prospect;
(2) preparation technology of sulfonated graphene metal-salt solid polymer electrolyte of the present invention is simple, easy to implement and regulation and control, and reaction conditions is gentle, and raw material sources are extensive, are convenient to large-scale production.
Accompanying drawing explanation
Fig. 1 is the SEM figure (pattern of sulfonated graphene lithium salts solid polymer electrolyte prepared by embodiment 2 ~ 5 is similar to Example 1, not shown herein) of sulfonated graphene lithium salts solid polymer electrolyte prepared by embodiment 1;
Fig. 2 is the SEM figure of graphene oxide lithium salts solid polymer electrolyte prepared by reference examples 1;
Fig. 3 is graphene oxide lithium salts solid polymer electrolyte prepared by the sulfonated graphene lithium salts solid polymer electrolyte prepared with embodiment 1 ~ 5 and the reference examples 1 electrochemical alternate impedance spectrum figure that is working electrode;
Fig. 4 be the graphene oxide lithium salts solid polymer electrolyte prepared of the sulfonated graphene lithium salts solid polymer electrolyte prepared using embodiment 1 ~ 5 and reference examples 1 as ionogen, and the linear voltammetric scan CV graphic representation using lithium sheet as working electrode;
Fig. 5 be the lithium ion battery of graphene oxide lithium salts solid polymer electrolyte prepared of the sulfonated graphene lithium salts solid polymer electrolyte prepared based on embodiment 1 ~ 5 and reference examples 1 under 1C discharge-rate, the specific discharge capacity contrast figure after 100 circulations.
Embodiment
Below in conjunction with some embodiments and accompanying drawing, more specific detail is done to technical scheme of the present invention, but it should not form any restriction to protection scope of the present invention.
The various raw materials addressed in following embodiment all can be obtained by market approach, some of them raw material, the suitable method self-control that such as sulfonated graphene also can be known according to those skilled in the art (such as consults CN103539105A, CN103359728A, NanoLetters, 2008,8 (6): 1679 documents such as – 1682 grade), and all kinds of testing apparatuss related to, all can select industry know and usual model.
The preparation method of this sulfonated graphene metal-salt solid polymer electrolyte of embodiment 1 comprises:
S1, sulfonated graphene is dispersed in DMSO, forms the sulfonated graphene solution that concentration is 0.1500g/L;
S2, in described sulfonated graphene solution, add Lithium Oxide 98min or lithium hydroxide in an inert atmosphere, make Lithium Oxide 98min or the addition of lithium hydroxide in sulfonated graphene solution be 0.3g/L, and at room temperature stirring reaction 6h, obtain sulfonated graphene lithium salt solution;
S3, in described sulfonated graphene lithium salt solution, add polyvinyl alcohol, the polymerization degree is 300 ~ 300,000, makes the addition of polyvinyl alcohol in sulfonated graphene lithium salt solution be 1g/L, and at 85 DEG C of stirring reaction 24h, obtain sulfonated graphene lithium salts solid polymer electrolyte solution;
S4, by described sulfonated graphene lithium salts solid polymer electrolyte solution 185 DEG C of oven dry, obtain sulfonated graphene lithium salts solid polymer electrolyte.
The preparation method of this sulfonated graphene metal-salt solid polymer electrolyte of embodiment 2 comprises:
S1, be dispersed in DMF with reference to the sulfonated graphene prepared by CN103539105A method, form the sulfonated graphene solution that concentration is 500g/L;
S2, in described sulfonated graphene solution, add Lithium Oxide 98min or lithium hydroxide in an inert atmosphere, make Lithium Oxide 98min or the addition of lithium hydroxide in sulfonated graphene solution be 30g/L, and at room temperature stirring reaction 1h, obtain sulfonated graphene lithium salt solution;
S3, in described sulfonated graphene lithium salt solution, add polyvinylpyrrolidone, the addition of polyvinylpyrrolidone in sulfonated graphene lithium salt solution is made to be 100g/L, and at 40 DEG C of stirring reaction 1h, obtain sulfonated graphene lithium salts solid polymer electrolyte solution;
S4, by described sulfonated graphene lithium salts solid polymer electrolyte solution 200 DEG C of oven dry, obtain sulfonated graphene lithium salts solid polymer electrolyte.
The preparation method of this sulfonated graphene lithium salts solid polymer electrolyte of embodiment 3 comprises:
S1, sulfonated graphene is dispersed in DMAC, forms the sulfonated graphene solution that concentration is 100g/L;
S2, in described sulfonated graphene solution, add Lithium Oxide 98min or lithium hydroxide in an inert atmosphere, make Lithium Oxide 98min or the addition of lithium hydroxide in sulfonated graphene solution be 10g/L, and at room temperature stirring reaction 4h, obtain sulfonated graphene lithium salt solution;
S3, in described sulfonated graphene lithium salt solution, add polyglycerol, make the addition of polyglycerol in sulfonated graphene lithium salt solution be 50g/L, and at 65 DEG C of stirring reaction 14h, obtain sulfonated graphene lithium salts solid polymer electrolyte solution;
S4, by described sulfonated graphene lithium salts solid polymer electrolyte solution 170 DEG C of oven dry, obtain sulfonated graphene lithium salts solid polymer electrolyte.
Embodiment 4 the present embodiment is substantially the same manner as Example 1, but using EC as organic solvent, using polyoxyethylene glycol as solid polymer electrolyte.
Embodiment 5 the present embodiment is substantially the same manner as Example 2, but using PC as organic solvent, using Mierocrystalline cellulose as solid polymer electrolyte.
Reference examples 1
S1, be dispersed in DMSO by the graphene oxide standby according to Hummers legal system, forming concentration is the graphene oxide solution of 1.5g/L;
S2, in described graphene oxide solution, add Lithium Oxide 98min in an inert atmosphere, make the addition of Lithium Oxide 98min in graphene oxide solution be 3g/L, and at room temperature stirring reaction 12h;
S3, obtain in mixing solutions in S2 and add polyvinyl alcohol, the polymerization degree is 300 ~ 300,000, the addition of polyvinyl alcohol in mixing solutions is made to be 2g/L, and at 85 DEG C of stirring reaction 24h, obtain graphene oxide-lithium salts-solid polymer electrolyte solution, then in 105 DEG C of oven dry, obtain graphene oxide-lithium salts-solid polymer electrolyte.
Refer to shown in Fig. 1 and Fig. 2, with SEM, the surface topography of embodiment 1-5 and reference examples 1 product is observed respectively, can know: the sulfonated graphene metal-salt that embodiment 1-5 obtains is dispersed in solid state electrolyte, and in reference examples 1 there is agglomeration in various degree in functionalization graphene.
Refer to shown in Fig. 3 and Fig. 4, respectively to the ionic conductivity of embodiment 1-5 and reference examples 1 product, electrochemical window etc. are tested, and can know: sulfonated graphene metal-salt solid state electrolyte ionic conductivity about 7.86 ~ 12.78 × 10
-3s/cm, electrochemical window is about 5.0V ~ 5.9V, and solid state electrolyte specific conductivity about 7.31 × 10 prepared by reference examples 1
-3s/cm, electrochemical window is about 4.8V only.
Application examples
The typical products obtained with embodiment 1-5 and reference examples 1 respectively builds lithium ion battery (with reference to SolidStareIonics, 2000,135:33-45), and performance of lithium ion battery is tested, as shown in Figure 5, can find, adopt sulfonated graphene lithium salts solid polymer electrolyte of the present invention, the specific discharge capacity that lithium ion battery tool is higher can be made, and sulfonated graphene lithium salts solid polymer electrolyte of the present invention also has better, with the chemistry of electrode materials and electrochemistry consistency.
It should be noted that, disclosed is the multiple of preferred embodiment, the change of every local or modification and come from technological thought of the present invention and be easy to by the people that has the knack of this technology to know by inference, all do not depart from patent right scope of the present invention.
Claims (15)
1. a sulfonated graphene metal-salt solid polymer electrolyte, it is characterized in that comprising containing sulfonic sulfonated graphene metal-salt and with the solid polymer electrolyte of described sulfonated graphene metal-salt by the hydroxyl of covalent bonds, described sulfonated graphene metal-salt is primarily of sulfonated graphene and the metallic compound composition being incorporated into sulfonated graphene surface by ionic linkage.
2. a preparation method for sulfonated graphene metal-salt solid polymer electrolyte, is characterized in that comprising:
S1, sulfonated graphene is dispersed in organic solvent, forms the sulfonated graphene solution that concentration is 0.1500g/L ~ 500g/L;
S2, in described sulfonated graphene solution, add metallic compound in an inert atmosphere, and at room temperature stirring reaction 1h ~ 6h, obtain sulfonated graphene metal salt solution;
S3, in described sulfonated graphene metal salt solution, add solid polymer electrolyte, and at 40 DEG C ~ 85 DEG C stirring reaction 1h ~ 24h, obtain sulfonated graphene metal-salt solid polymer electrolyte solution;
S4, drying treatment is carried out to described sulfonated graphene metal-salt solid polymer electrolyte solution, obtain described sulfonated graphene metal-salt solid polymer electrolyte.
3. the preparation method of sulfonated graphene metal-salt solid polymer electrolyte according to claim 2, it is characterized in that, step S4 comprises: by described sulfonated graphene metal-salt solid polymer electrolyte solution 85 DEG C ~ 200 DEG C oven dry, obtain described sulfonated graphene metal-salt solid polymer electrolyte.
4. the preparation method of sulfonated graphene metal-salt solid polymer electrolyte according to claim 2, it is characterized in that described organic solvent comprises dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, ethyl cellulose, polycarbonate, any one or two or more combinations in Methyl ethyl carbonate.
5. the preparation method of sulfonated graphene metal-salt solid polymer electrolyte according to claim 2, it is characterized in that, described metallic compound comprises Lithium Oxide 98min and/or lithium hydroxide, sodium oxide and/or sodium hydroxide, potassium oxide and/or potassium hydroxide, magnesium oxide and/or magnesium hydroxide, calcium oxide and/or calcium hydroxide, any one or two or more combinations in aluminum oxide and/or aluminium hydroxide.
6. the preparation method of sulfonated graphene metal-salt solid polymer electrolyte according to claim 2 or 5, it is characterized in that, the addition of metallic compound described in step S2 in sulfonated graphene solution is 0.3g/L ~ 30g/L.
7. the preparation method of sulfonated graphene metal-salt solid polymer electrolyte according to claim 2, it is characterized in that the radial dimension of described sulfonated graphene is 0.05 μm ~ 100 μm, thickness is 0.5nm ~ 20nm, and wherein sulfonic content is expressed as 12:1 ~ 3:1 with the mol ratio of carbon sulphur.
8. the preparation method of sulfonated graphene metal-salt solid polymer electrolyte according to claim 2, is characterized in that the mol ratio of metallic element in sulfonate radical and described metallic compound in described sulfonated graphene is 1:1 ~ 5:1.
9. the preparation method of sulfonated graphene metal-salt solid polymer electrolyte according to claim 2, it is characterized in that, described solid polymer electrolyte is at least selected from poly-hydroxy base polymer, and described poly-hydroxy base polymer comprises polyvinyl alcohol, polyoxyethylene glycol, polyglycerol, polyvinylpyrrolidone, Mierocrystalline cellulose, chitosan, cyclodextrin, any one or two or more combinations in phytic acid.
10. the preparation method of sulfonated graphene metal-salt solid polymer electrolyte according to claim 2 or 9, it is characterized in that, the addition of solid polymer electrolyte described in step S3 in sulfonated graphene lithium salt solution is 1g/L ~ 100g/L.
The preparation method of 11. sulfonated graphene metal-salt solid polymer electrolytes according to claim 2, is characterized in that, in described sulfonated graphene, in sulfonate radical and described solid polymer electrolyte, the mol ratio of hydroxyl is 5:1 ~ 25:1.
The 12. sulfonated graphene metal-salt solid polymer electrolytes that according to any one of claim 2-11 prepared by method, its ionic conductivity reaches 10
-2the S/cm order of magnitude, electrochemical window is 5.4V ~ 6.2V.
The application of sulfonated graphene metal-salt solid polymer electrolyte described in 13. claims 1 or 12 in preparation electrochemistry and/or physics energy storage device.
14. 1 kinds of electrochemistry and/or physics energy storage device, it is characterized in that comprising sulfonated graphene metal-salt solid polymer electrolyte described in claim 1 or 12, described electrochemistry and/or physics energy storage device comprise electrical condenser or battery, and described electrical condenser comprises electrolytic condenser, ultracapacitor or hybrid super capacitor, described battery lithium ion battery, sodium-ion battery, kalium ion battery, Magnesium ion battery, calcium ion battery, aluminum ion battery, fuel cell or fuel sensitization solar battery.
15. 1 kinds of batteries, comprise positive and negative plate and be placed in the barrier film between positive plate and negative plate, it is characterized in that the sulfonated graphene metal-salt solid polymer electrolyte also comprised described in claim 1 or 12, described battery lithium ion battery, sodium-ion battery, kalium ion battery, Magnesium ion battery, calcium ion battery or aluminum ion battery.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017127694A1 (en) * | 2016-01-22 | 2017-07-27 | California Institute Of Technology | Vertical carbon nanotube and lithium ion battery chemistries |
| CN107658478A (en) * | 2017-09-22 | 2018-02-02 | 北京协同创新研究院 | A kind of all-vanadium flow battery barrier film and preparation method thereof |
| CN108075088A (en) * | 2016-11-10 | 2018-05-25 | 苏州高通新材料科技有限公司 | Lithium battery diaphragm, its preparation method and the application of the lithium salts containing sulfonated graphene |
| CN108417888A (en) * | 2018-03-22 | 2018-08-17 | 上海力信能源科技有限责任公司 | A kind of no lithium salts modified graphene composite solid electrolyte material, dielectric film and preparation method thereof |
| CN110970230A (en) * | 2018-09-30 | 2020-04-07 | 天津大学 | Hydrogel polymerized in situ on surface of phytic acid/sulfuric acid gel, preparation method thereof and application thereof in flexible supercapacitor |
| CN112886009A (en) * | 2019-11-29 | 2021-06-01 | 恒大新能源技术(深圳)有限公司 | Conductive agent, preparation method thereof, electrode and secondary battery |
| CN114335714A (en) * | 2021-12-31 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Single lithium ion polymer electrolyte membrane and battery comprising same |
| CN115863745A (en) * | 2022-03-08 | 2023-03-28 | 广西柳工机械股份有限公司 | Polymer/graphene composite solid electrolyte membrane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102891335A (en) * | 2012-10-11 | 2013-01-23 | 同济大学 | Preparation method of full-solid-state nano composite polymer electrolyte |
| CN104528690A (en) * | 2015-01-13 | 2015-04-22 | 苏州高通新材料科技有限公司 | Porous carbon microsphere with surface covered with graphene, and preparing method and application of porous carbon microsphere |
-
2015
- 2015-07-08 CN CN201510396951.XA patent/CN105218992B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102891335A (en) * | 2012-10-11 | 2013-01-23 | 同济大学 | Preparation method of full-solid-state nano composite polymer electrolyte |
| CN104528690A (en) * | 2015-01-13 | 2015-04-22 | 苏州高通新材料科技有限公司 | Porous carbon microsphere with surface covered with graphene, and preparing method and application of porous carbon microsphere |
Non-Patent Citations (1)
| Title |
|---|
| JEN-MING YANG 等: "Preparation of graphene-based poly(vinyl alcohol)/chitosan nanocomposites membrane for alkaline solid electrolytes membrane", 《JOURNAL OF MEMBRANE SCIENCE》 * |
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| US11056712B2 (en) | 2016-01-22 | 2021-07-06 | California Institute Of Technology | Vertical carbon nanotube and lithium ion battery chemistries, articles, architectures and manufacture |
| CN108075088A (en) * | 2016-11-10 | 2018-05-25 | 苏州高通新材料科技有限公司 | Lithium battery diaphragm, its preparation method and the application of the lithium salts containing sulfonated graphene |
| CN107658478A (en) * | 2017-09-22 | 2018-02-02 | 北京协同创新研究院 | A kind of all-vanadium flow battery barrier film and preparation method thereof |
| CN108417888A (en) * | 2018-03-22 | 2018-08-17 | 上海力信能源科技有限责任公司 | A kind of no lithium salts modified graphene composite solid electrolyte material, dielectric film and preparation method thereof |
| CN110970230A (en) * | 2018-09-30 | 2020-04-07 | 天津大学 | Hydrogel polymerized in situ on surface of phytic acid/sulfuric acid gel, preparation method thereof and application thereof in flexible supercapacitor |
| CN112886009A (en) * | 2019-11-29 | 2021-06-01 | 恒大新能源技术(深圳)有限公司 | Conductive agent, preparation method thereof, electrode and secondary battery |
| CN112886009B (en) * | 2019-11-29 | 2022-06-24 | 恒大新能源技术(深圳)有限公司 | Conductive agent, preparation method thereof, electrode and secondary battery |
| CN114335714A (en) * | 2021-12-31 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Single lithium ion polymer electrolyte membrane and battery comprising same |
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