CN107293798A - Cyanethyl cellulose film, cyanethyl cellulose gel polymer electrolyte and preparation method thereof - Google Patents
Cyanethyl cellulose film, cyanethyl cellulose gel polymer electrolyte and preparation method thereof Download PDFInfo
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- CN107293798A CN107293798A CN201710558243.0A CN201710558243A CN107293798A CN 107293798 A CN107293798 A CN 107293798A CN 201710558243 A CN201710558243 A CN 201710558243A CN 107293798 A CN107293798 A CN 107293798A
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- Prior art keywords
- cyanethyl cellulose
- polymer electrolyte
- gel polymer
- cyanethyl
- film
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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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of cyanethyl cellulose film, cyanethyl cellulose gel polymer electrolyte and preparation method thereof.Cyanethyl cellulose is dissolved in solvent and forms solution, then drying and forming-film；Cyanethyl cellulose film is immersed and activated in electrolyte to gel；Remove and obtain cyanethyl cellulose gel polymer electrolyte after gel surface excess electrolyte.Cyanethyl cellulose gel polymer electrolyte prepared by the present invention, heat resistance and good corrosion resistance, raw material sources are extensively and with recyclability and biodegradable；The tensile strength of cyanethyl cellulose film is more than 25MPa, and with 700% 1300% pick up, cyanethyl cellulose gel polymer electrolyte conductivity at room temperature reaches 10‑3S/cm grades, lithium ion transference number is more than 0.7, and electrochemical stability window is more than 4.8V；The cyanethyl cellulose gel polymer electrolyte of the present invention, preparation method is simple, practical, it is easy to operate.
Description
Technical field
The present invention relates to a kind of battery material, and in particular to a kind of cyanethyl cellulose for lithium rechargeable battery
Film, cyanethyl cellulose gel polymer electrolyte film and preparation method thereof.
Background technology
As new generation of green high-energy rechargeable battery, lithium ion battery and traditional lead-acid accumulator, Ni-MH battery etc. two
Primary cell is compared, high with monomer battery voltage, and specific energy is big, memory-less effect, pollution-free self discharge is small, have extended cycle life
Advantage, is widely applied in the portable type electronic products such as notebook computer, smart mobile phone, digital camera, dynamic
Power field of batteries also has wide development space.The lithium ion battery of traditional commerce typically uses inflammable organic liquor
, there is the security risks such as leakage and combustion explosion in use in body electrolyte.Polymer Li-ion battery is as in recent years
Study hotspot, have the advantages that with low cost, processing is simple and controlled shape, can effectively be solved compared to liquid lithium ionic cell
Certainly the safety problem such as leakage and combustion explosion, has wide in fields such as portable electric appts, electric automobile and space flight and aviation
Application prospect.
Polymer dielectric is different with composition according to form, can be divided into full solid state polymer electrolyte (SPE) and gel is poly-
Polymer electrolyte (GPE).The former is only made up of polymer and lithium salts, haves the shortcomings that conductivity at room temperature is low, is extremely difficult to
Actual use demand.Typically by adding small molecule plasticizer with reduce polymer glass transition temperature and improve strand
Compliance, obtain gel polymer electrolyte.Gel polymer electrolyte can reach the room temperature similar to liquid electrolyte
Ionic conductivity, and help to preserve electrolyte, it is possible to reduce the risk of electrolyte leakage, improves security performance, has simultaneously
There are plasticity and processing type strong, the advantages of controlled shape.It is PEO (PEO) base, polypropylene to study at this stage more
Nitrile (PAN) base, polymethyl methacrylate (PMMA) base, polyvinylidene fluoride (PVDF) and its copolymer matrix gelatin polymer electricity
Xie Zhi.Although these gel polymer electrolytes are with good performance, it derives from non-renewable fossil energy, system
Standby complicated, biological degradability is poor.Attention with the exhaustion and people of fossil energy to environmental protection, finds a kind of renewable, nothing
The polymer electrolyte of pollution is significant.
Cellulose derivative have raw material sources it is wide, renewable, nontoxic, it is degradable many advantages, such as, in polymer electrolytic
There is good application prospect in matter.Highly cyanoethylated cellulose (CEC) is a kind of organic molten fiber type of high-k
Plain derivative, high-k helps lend some impetus to the dissolving of lithium salts, increases carrier concentration, so as to improve ionic conductivity, subtracts
Weak concentration polarization phenomenon, reduces the formation of Li dendrite, and CEC heat resistance good corrosion resistances, for improving polymer Li-ion electricity
The performance in pond has positive meaning.Cyanethyl cellulose gel polymer electrolyte material is also rarely reported.
The content of the invention
It is an object of the invention to provide a kind of good mechanical property, pick up are high, excellent electrical property for lithium ion secondary
The cyanethyl cellulose film of battery, cyanethyl cellulose gel polymer electrolyte and preparation method thereof.
The present invention is achieved by the following technical solution：
Cyanethyl cellulose method for preparing gel polymer electrolyte for lithium rechargeable battery includes step：
A. cyanethyl cellulose is dissolved in solvent and forms solution, then drying and forming-film；
B. cyanethyl cellulose film is immersed and activated in electrolyte to gel；
C. remove after gel surface excess electrolyte and obtain cyanethyl cellulose gel polymer electrolyte film.
Further, in above-mentioned cyanethyl cellulose method for preparing gel polymer electrolyte, described in the step B
Electrolyte is the organic solution of following lithium salts.
Further, in above-mentioned cyanethyl cellulose method for preparing gel polymer electrolyte, the lithium salts is hexafluoro
Lithium phosphate, lithium perchlorate, LiBF4, one or more mixing of hexafluoroarsenate lithium.
Further, in above-mentioned cyanethyl cellulose method for preparing gel polymer electrolyte, the dissolving lithium
The organic solvent of salt is in ethylene carbonate, diethyl carbonate, methyl ethyl ester, dimethyl carbonate, propene carbonate
One or more mixing.
Further, in above-mentioned cyanethyl cellulose method for preparing gel polymer electrolyte, described in the step A
The substitution value of cyanethyl cellulose is not less than 2.2.
Further, in above-mentioned cyanethyl cellulose method for preparing gel polymer electrolyte, described in the step A
Solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO).
The present invention also provides a kind of cyanethyl cellulose gel polymer electrolyte and cyanethyl cellulose film, and it is according to such as
Upper described preparation method is prepared.
The present invention has the advantages that：
1. the cyanethyl cellulose gel polymer electrolyte of the present invention, heat resistance and good corrosion resistance, raw material sources are wide
It is general and with recyclability and biodegradable；
2. the cyanethyl cellulose film that the present invention is provided, tensile strength is more than 25MPa, the imbibition with 700-1300%
Rate；The conductivity at room temperature for the cyanethyl cellulose gel polymer electrolyte that the present invention is provided reaches 10-3S/cm grades, lithium from
Sub- transport number is more than 0.7, and electrochemical stability window is more than 4.8V；
3. the cyanethyl cellulose gel polymer electrolyte of the present invention, only by cyanethyl cellulose and lithium salt electrolyte two
Part is constituted, and composition is simple；
4. the cyanethyl cellulose film that the first step is prepared in the present invention, with can room temperature environment preserve and storage it is excellent
Gesture, and by regulating and controlling the soak time of film in the electrolytic solution, the cyanogen of different mechanical strengths and different ions electrical conductivity can be obtained
Ethyl cellulose gel polymer electrolyte, flexibility is strong.
5. preparation process is simple and practical, and need not be related to polymerization crosslinking reaction, help to reduce cost, improve efficiency.
Embodiment
With reference to specific embodiment, the present invention will be further described.The embodiment is only being preferable to carry out for the present invention
Example, is not intended to limit the invention, for those skilled in the art, the present invention can have various changes and change
Change.Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., should be included in the present invention
Protection domain within.
Embodiment 1
1g substitution values are dissolved in formation clear solution in 50gN, dinethylformamide (DMF) for 2.25 CEC, taken
25g solution is poured into diameter 9cm culture dish, is put into 12h in 80 DEG C of baking ovens and is dried, obtains the CEC films that thickness is about 85 μm.Cut out
Into after suitable dimension, dried CEC films are immersed into lithium perchlorate (LiClO in glove box4)：Ethylene carbonate (EC)：Carbon
Acid propylene ester (PC)=1：1：2h is activated in 1 electrolyte to gel state, excess surface electrolyte is gently dried with filter paper, is obtained
To CEC gel polymer electrolytes.
Embodiment 2
1g substitution values are dissolved in formation clear solution in 50gN, N- dimethyl acetamides (DMAc) for 2.35 CEC, taken
25g solution is poured into diameter 9cm culture dish, is put into 12h in 80 DEG C of baking ovens and is dried, obtains the CEC films that thickness is about 85 μm.Cut out
Into after suitable dimension, dried CEC films are immersed into lithium hexafluoro phosphate (LiPF in glove box6)：Ethylene carbonate (EC)：Carbon
Dimethyl phthalate (DMC)：Methyl ethyl ester (EMC)=1：1：1：6h is activated in 1 electrolyte to gel state, it is light with filter paper
Dry excess surface electrolyte is dabbed, CEC gel polymer electrolytes are obtained.
Embodiment 3
1g substitution values are dissolved in formation clear solution in 50gN, dinethylformamide (DMF) for 2.5 CEC, taken
25g solution is poured into diameter 9cm culture dish, is put into 12h in 80 DEG C of baking ovens and is dried, obtains the CEC films that thickness is about 85 μm.Cut out
Into after suitable dimension, dried CEC films are immersed into LiBF4 (LiBF in glove box4)：Ethylene carbonate (EC)：Carbon
Dimethyl phthalate (DMC)=1：1：6h is activated in 1 electrolyte to gel state, excess surface electrolyte is gently dried with filter paper,
Obtain CEC gel polymer electrolytes.
Embodiment 4
1g substitution values are dissolved in formation clear solution in 30g DMAs (DMAc) for 2.66 CEC,
Take 15g solution to pour into diameter 9cm culture dish, be put into 12h in 80 DEG C of baking ovens and dry, obtain the CEC films of about 75 μm of thickness.Cut out
Into after suitable dimension, dried CEC films are immersed into lithium hexafluoro phosphate (LiPF in glove box6)：Ethylene carbonate (EC)：Carbon
Dimethyl phthalate (DMC)=1：1：6h is activated in 1 electrolyte to gel state, the electrolysis of excess surface is gently dried with filter paper
Liquid, obtains CEC gel polymer electrolytes.
Embodiment 5
1g substitution values are dissolved in formation clear solution in 40g DMFs (DMF) for 2.75 CEC, taken
20g solution is poured into diameter 9cm culture dish, is put into 12h in 80 DEG C of baking ovens and is dried, obtains the CEC films of about 80 μm of thickness.It is cut into
After suitable dimension, dried CEC films are immersed into lithium hexafluoro phosphate (LiPF in glove box6)：Ethylene carbonate (EC)：Carbonic acid
Methylethyl ester (EMC)=1：1：6h is activated in 1 electrolyte to gel state, the electrolysis of excess surface is gently dried with filter paper
Liquid, obtains CEC gel polymer electrolytes.
CEC films obtained by embodiment 1 to embodiment 5 are through performance test：Tensile strength is all higher than 25MPa, with 700-
1300% pick up；CEC gel polymer electrolytes obtained by embodiment 1 to embodiment 5 are through performance test：Room temperature condition
Think, its ionic conductivity reaches 10-3S/cm grades, lithium ion transference number is all higher than 0.7, and electrochemical stability window is all higher than
4.8V。
Claims (8)
1. cyanethyl cellulose method for preparing gel polymer electrolyte, it is characterised in that including step：
A. cyanethyl cellulose is dissolved in solvent and forms solution, then drying and forming-film produces cyanethyl cellulose film；
B. cyanethyl cellulose film is immersed and activated in electrolyte to gel；
C. remove after gel surface excess electrolyte and obtain cyanethyl cellulose gel polymer electrolyte.
2. cyanethyl cellulose method for preparing gel polymer electrolyte according to claim 1, it is characterised in that
Electrolyte described in the step B is the organic solution of following lithium salts.
3. cyanethyl cellulose method for preparing gel polymer electrolyte according to claim 2, it is characterised in that
The lithium salts is one or more mixing of lithium hexafluoro phosphate, lithium perchlorate, LiBF4, hexafluoroarsenate lithium.
4. cyanethyl cellulose method for preparing gel polymer electrolyte according to claim 2, it is characterised in that
The organic solvent of the dissolving lithium salts is ethylene carbonate, diethyl carbonate, methyl ethyl ester, carbonic acid diformazan
One or more mixing in ester, propene carbonate.
5. cyanethyl cellulose method for preparing gel polymer electrolyte according to claim 1, it is characterised in that
The substitution value of cyanethyl cellulose described in the step A is not less than 2.2.
6. cyanethyl cellulose method for preparing gel polymer electrolyte according to claim 1, it is characterised in that
Solvent described in the step A is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO).
7. a kind of cyanethyl cellulose gel polymer electrolyte, it is characterised in that such as any one institute in claim 1 to 6
It is prepared by the preparation method stated.
8. a kind of cyanethyl cellulose film, it is characterised in that the preparation method system as described in any one in claim 1 to 6
It is standby.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710558243.0A CN107293798A (en) | 2017-07-10 | 2017-07-10 | Cyanethyl cellulose film, cyanethyl cellulose gel polymer electrolyte and preparation method thereof |
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| CN201710558243.0A CN107293798A (en) | 2017-07-10 | 2017-07-10 | Cyanethyl cellulose film, cyanethyl cellulose gel polymer electrolyte and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113299981A (en) * | 2020-02-21 | 2021-08-24 | 广州天赐高新材料股份有限公司 | Solid polymer electrolyte membrane, preparation method and application thereof |
| CN116190777A (en) * | 2022-12-20 | 2023-05-30 | 重庆太蓝新能源有限公司 | Cellulose-based eutectic gel electrolyte, preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113299981A (en) * | 2020-02-21 | 2021-08-24 | 广州天赐高新材料股份有限公司 | Solid polymer electrolyte membrane, preparation method and application thereof |
| CN116190777A (en) * | 2022-12-20 | 2023-05-30 | 重庆太蓝新能源有限公司 | Cellulose-based eutectic gel electrolyte, preparation method and application thereof |
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Application publication date: 20171024 |