CN114106378A - Preparation method of natural cellulose-based polymer electrolyte - Google Patents
Preparation method of natural cellulose-based polymer electrolyte Download PDFInfo
- Publication number
- CN114106378A CN114106378A CN202111405796.5A CN202111405796A CN114106378A CN 114106378 A CN114106378 A CN 114106378A CN 202111405796 A CN202111405796 A CN 202111405796A CN 114106378 A CN114106378 A CN 114106378A
- Authority
- CN
- China
- Prior art keywords
- natural cellulose
- polymer electrolyte
- electrolyte
- cellulose
- salt
- 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.)
- Pending
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920003174 cellulose-based polymer Polymers 0.000 title claims description 10
- 229920002678 cellulose Polymers 0.000 claims abstract description 78
- 239000001913 cellulose Substances 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000003792 electrolyte Substances 0.000 claims abstract description 36
- 229920006254 polymer film Polymers 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 25
- 239000012528 membrane Substances 0.000 claims description 18
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 claims description 17
- -1 lithium halide Chemical class 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 239000002608 ionic liquid Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000010041 electrostatic spinning Methods 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 claims description 4
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 4
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
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- 238000007731 hot pressing Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 2
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-UHFFFAOYSA-N 0.000 claims description 2
- PWGVOCGNHYMDLS-UHFFFAOYSA-N 3-(2-methoxyethoxy)propan-1-amine Chemical compound COCCOCCCN PWGVOCGNHYMDLS-UHFFFAOYSA-N 0.000 claims description 2
- CMWINYFJZCARON-UHFFFAOYSA-N 6-chloro-2-(4-iodophenyl)imidazo[1,2-b]pyridazine Chemical compound C=1N2N=C(Cl)C=CC2=NC=1C1=CC=C(I)C=C1 CMWINYFJZCARON-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 229910021201 NaFSI Inorganic materials 0.000 claims description 2
- 229910019398 NaPF6 Inorganic materials 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 2
- KVFIZLDWRFTUEM-UHFFFAOYSA-N potassium;bis(trifluoromethylsulfonyl)azanide Chemical compound [K+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F KVFIZLDWRFTUEM-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 2
- PUQLFUHLKNBKQQ-UHFFFAOYSA-L calcium;trifluoromethanesulfonate Chemical compound [Ca+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F PUQLFUHLKNBKQQ-UHFFFAOYSA-L 0.000 claims 1
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims 1
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 12
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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Abstract
The invention belongs to the fields of high molecular materials and electrochemical energy storage, and particularly relates to preparation of a natural cellulose polymer electrolyte, and application of the polymer electrolyte in batteries, capacitors and fuel cells. The natural cellulose polymer electrolyte is composed of a natural cellulose polymer film and a plasticizer containing an electrolyte salt. The invention relates to dissolution of natural cellulose, film formation, preparation of polymer electrolyte and assembly of energy storage devices. The natural cellulose dissolving preparation method has the advantages of simple process, low cost and environment-friendly preparation process. The prepared gel polymer electrolyte has high conductivity, wide electrochemical window, high ion migration number and good compatibility with electrode materials, can effectively inhibit the growth of metal dendrites, and obviously improves the cycle stability and rate capability of electrochemical energy storage devices such as batteries and the like. The polymer electrolyte can be used in a solid electrochemical energy storage system with high energy density, large capacity, high power and high safety.
Description
Technical Field
The invention relates to the technical field of high molecules and electrochemical energy storage, in particular to a natural cellulose polymer electrolyte for a solid energy storage system and a preparation method thereof.
Background
Since the lithium ion battery is commercialized in the last 90 th century, the lithium ion battery is widely applied to portable electronic products such as mobile phones, tablet computers, mobile power supplies and the like, plays a very important role in an electric automobile system as a power battery, and has gradually shown application potential in an intelligent power grid system as an energy storage battery.
However, since the lithium ion battery widely uses an organic liquid electrolyte (electrolyte salt and a small amount of additive are dissolved in a flammable organic solvent) and a polyolefin microporous membrane, the battery is very easy to have safety accidents such as fire, explosion and the like under the conditions of large-rate charging and discharging or abuse and the like. With the development of energy storage industry, lithium resources are gradually exhausted, researchers turn research into sodium with properties close to those of lithium, and sodium has high natural reserves, low price and higher theoretical capacity (1165mAh g)-1) And the low oxidation-reduction potential (-2.714V vs SHE) and the like, and becomes a substitute for the lithium metal negative electrode. Sodium metal cathodes, however, also suffer from a number of problems. Sodium is highly chemically active and readily reacts with liquid electrolytes, resulting in decomposition of the liquid electrolytes and formation of unstable by-products, which results in low coulombic efficiency. The SEI film generated by the contact of the liquid electrolyte and the sodium cathode has low mechanical strength and is easy to break, the growth of dendritic crystals is difficult to stop, and the potential safety hazard is still difficultTo put an end to.
In order to improve the safety of electrochemical energy storage devices such as batteries, Gel Polymer Electrolytes (GPEs) have dual properties of liquid electrolytes and solid electrolytes (high safety, strong plasticity, high conductivity, wide electrochemical window, good compatibility with electrode materials, and the like), and are widely paid attention to by researchers. The research on polymer electrolytes is currently mainly focused on the following materials: polyethers (mainly PEO), Polyacrylonitriles (PAN), Polymethacrylates (PMMA), polyvinylidene fluorides (PVDF), and the like. However, the preparation process of the materials is complex, the price is high, and the wide application of the polymer electrolyte in electrochemical energy storage devices such as batteries and the like is greatly limited. The development of low-cost, excellent-performance and electrolyte-gelling polymer materials has become a hot point in the research of polymer electrolytes.
Cellulose is a natural high molecular material with rich sources and wide distribution, is a macromolecular polysaccharide, is insoluble in water and common organic solvents, and is a main component of plant cell walls. Cellulose is the most abundant natural organic matter in the world, accounts for more than 50% of the carbon content in the plant kingdom, and is widely present in wood, weeds, cotton, hemp, wheat straws, rice straws and bagasse. The cellulose is environment-friendly, low in price and high in thermal stability, can solve the pollution problem of the traditional electrolyte, further reduces the cost of electrochemical energy storage devices such as chemical batteries and the like, and is an excellent choice of polymer electrolyte materials. However, the natural cellulose has a large number of hydrogen bonds, which makes it difficult to dissolve in common solvents to form a uniform solution, resulting in a great limitation in the use of the natural cellulose. Research in recent years finds that the hydrogen bonds in natural cellulose molecules can be opened by selecting a specific solvent system, so that the natural cellulose is dissolved, and further the cellulose is modified.
Common dissolving systems of natural cellulose include an NMMO (N-methylmorpholine-N-oxide) system, a lithium halide/amide system, an ionic liquid, an alkaline water system, an alkaline/urea system and other novel solvents. The active N-O dipole and oxygen group in NMMO can break hydrogen bonds in cellulose molecules, so that the cellulose molecules are dissolved in the NMMO solution system(ii) a Protonated hydroxyl groups of cellulose with halide ions (X)-) Form strong hydrogen bonds, Li+The ions are dissolved by the amide solution molecules when Li+-X-When the ion pair is split, a hydrogen bond network among cellulose molecules can be damaged, and finally, cellulose chains are dispersed on a molecular level to obtain a uniform solution; anions of the ionic liquid are connected to hydroxyl groups at the edges of the cellulose molecular beams to form negatively charged complexes, and then cations are inserted between the molecular beams, so that the separation of cellulose molecules is promoted, and the cellulose is dissolved; the hydroxide solution forms new hydrogen bonds with the cellulose at low temperature, and the urea hydrate wraps around the hydroxide-hydrogen bond-cellulose to form an inclusion compound, so that the cellulose is dissolved.
After dissolving the cellulose, films can be prepared by a variety of methods. The freeze drying technology is a method for drying a frozen sample by directly sublimating ice into steam under the conditions of low temperature (-10 ℃ to-70 ℃) and low pressure (1.3 to 20Pa) by utilizing the principle of ice crystal sublimation. The natural cellulose polymer electrolyte prepared by the method has a net structure, can effectively prevent the uneven deposition of metal in the circulation process of electrochemical energy storage devices such as batteries and the like, and has good inhibition effect on the growth of metal dendrites; the pouring method is to volatilize the solvent in the solution under the high-temperature heating condition, and prepare a dry sample by physically crosslinking the macromolecules in the solution. The natural cellulose polymer electrolyte prepared by the method has a compact and flat structure, can effectively inhibit the growth of metal dendrites, and improves the cycle stability of electrochemical energy storage devices such as batteries and the like; the electrostatic spinning method is that direct current high voltage is applied between polymer solution and a collecting device, so that the polymer solution carries thousands to tens of thousands of volts of high voltage static electricity, when the electric field force is large enough, charged polymer liquid drops overcome the surface tension to form jet trickle, the trickle is evaporated and solidified along with a solvent in the jetting process and finally falls on the collecting device to form a fiber felt similar to non-woven fabrics, the diameter of spinning fibers can be from a few nanometers to hundreds of micrometers, the thickness of a formed film is controllable, the aperture is uniform, and the advantages in the aspect of preparing a high polymer film material are obvious; the phase inversion method refers to a process of converting a polymer solution with a continuous solvent system into a swellable three-dimensional macromolecular network gel. The process is that one liquid phase is added with a non-solvent and then is converted into two liquid phases. The solvent is then allowed to evaporate before the non-solvent, causing the non-solvent and polymer to increase in content, eventually resulting in polymer precipitation and film formation. The diaphragm prepared by the method has a three-dimensional network structure, and can effectively prevent the uneven deposition of metal ions in the circulation of electrochemical energy storage devices such as batteries and the like, thereby inhibiting the growth of metal dendrites; the Bellcore process is a process in which a plasticizer is added to a polymer solution to be uniformly dispersed in a solvent, and then the plasticizer is dissolved out of a polymer matrix using another solvent having a low boiling point, thereby forming a microporous polymer membrane. The diaphragm prepared by the method has a microporous structure with uniform size, and can effectively improve the ionic conductivity of electrochemical energy storage devices such as batteries and the like.
Disclosure of Invention
The invention aims to provide a natural cellulose gel polymer electrolyte for a solid energy storage system, and the obtained polymer electrolyte not only has high ion migration number, good mechanical property, high safety performance, stable chemical property, low production cost and wide electrochemical window, but also can be matched with common electrode materials and shows excellent electrochemical properties (low internal resistance, long cycle stability and excellent rate performance).
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing a natural cellulose-based polymer electrolyte, comprising the steps of:
(1) dissolving natural cellulose in an NMMO system, a lithium halide/amide system, ionic liquid, an alkali water system, an alkali/urea system and other novel solvent systems to obtain a uniform natural cellulose solution;
(2) preparing a natural cellulose polymer film by casting, coating, papermaking, hot pressing, screen printing, freeze drying, electrostatic spinning, phase inversion, impregnation, foaming and Bellcore methods, wherein the thickness of the film is controlled to be 5-500 mu m;
(3) placing the natural cellulose polymer film obtained in the step (2) in a vacuum drying oven, drying at the temperature of room temperature to 300 ℃, and removing trace solvent;
(4) and (3) soaking the dried compound obtained in the step (3) in an electrolyte in an anhydrous and oxygen-free environment for 1 minute to 24 hours to obtain the natural cellulose polymer electrolyte.
The dissolving process of the step (1) is to stir and dissolve for 0.5 to 12 hours at the temperature of 100 ℃.
The electrolyte in the step (4) can be added into the natural cellulose solution in the step (1), and the natural cellulose membrane prepared by the method only needs to be soaked in the solvent of the electrolyte in the step (4).
The step (4) of preparing the natural cellulose gel polymer electrolyte is carried out at room temperature, and the electrolyte imbibing time is between 1min and 24 h.
The electrolyte in the step (4) is formed by dissolving zinc salt, lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt and aluminum salt of electrolyte in carbonate, ether or pure water solvent or is ionic liquid, and the concentration is 0.1mol L-1-50mol L-1In the meantime.
The electrolyte adopted in the step (4) is zinc sulfate (ZnSO)4) Zinc acetate ((CH)3COO)2Zn), zinc triflate (Zn (CF)3SO3)2) Zinc chloride (ZnCl), zinc nitrate (Zn (NO)3)2) Lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium bistrifluoromethanesulfonylimide (LiFSI), sodium perchlorate (NaClO4), lithium hexafluorophosphate (NaPF6), sodium bistrifluoromethanesulfonylimide (NaTFSI), sodium sulfate (Na)2SO4) Sodium acetate (CH)3COONa), sodium bis (fluorosulfonyl) imide (NaFSI), potassium perchlorate (KClO)4) Potassium hexafluorophosphate (KPF)6) Potassium tetrafluoroborate (KBF)4) Potassium hexafluoroarsenate (KAsF)6) Potassium bistrifluoromethanesulfonylimide (KTFSI), potassium bistrifluoromethylsulfonyl imide (KN (CF)3SO2)2) Calcium hexafluorophosphate (Ca (PF)6)2) Calcium chloride (CaCl)2) Calcium sulfate (CaSO)4) Trifluoro benzene and trifluoro benzeneCalcium methanesulfonate ((CF)3SO3)2Ca), calcium perchlorate (Ca (ClO)4)2) Aluminum trifluoromethanesulfonate (Al (OTf)3) Aluminum chloride (AlCl)3) Aluminum nitrate (Al (NO)3)3) Aluminum sulfate (Al)2(SO4)3) One or more kinds of salt are mixed.
The electrolyte solvent adopted in the step (4) comprises carbonate, ether or pure water, such as one or more of ethylene carbonate, methyl ethyl carbonate, diethyl carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, ethylene glycol diether, tetrahydrofuran, dioxolane and pure water.
The cellulose polymer electrolyte raw material is natural cellulose, is macromolecular polysaccharide, is insoluble in water and common organic solvents, and is a main component of plant cell walls. Cellulose is the most abundant natural organic matter in the world, accounts for more than 50% of the carbon content in the plant kingdom, and is widely present in wood, weeds, cotton, hemp, wheat straws, rice straws and bagasse. The natural cellulose polymer electrolyte can be applied to different energy storage devices, such as fuel cells, chemical batteries, capacitors and the like according to the characteristics of different electrolyte salt-containing plasticizers; the natural cellulose can be dissolved by an NMMO (N-methylmorpholine-N-oxide) system, a lithium halide/amide system, ionic liquid, an alkaline water system, an alkaline/urea system and other novel solvents to prepare a solution; the cellulose polymer electrolyte can be prepared by casting, coating, papermaking, hot pressing, screen printing, freeze drying, electrostatic spinning, phase inversion, impregnation, foaming, Bellcore and other methods.
Active N-O dipoles and oxygen groups in the NMMO can break hydrogen bonds in cellulose molecules, so that the cellulose molecules are dissolved in an NMMO solution system; protonated hydroxyl groups of cellulose with halide ions (X)-) Form strong hydrogen bonds while Li+The ions are dissolved by the amide solution molecules. When Li is present+-X-When the ion pair is split, the hydrogen bond network between cellulose molecules is broken. Then, cellulose chains are dispersed at the molecular level to obtain a uniform solution; anion of ionic liquidsHydroxyl groups which are sub-linked to the edges of the cellulose molecular beams to form negatively charged complexes, and cations are subsequently inserted between the molecular beams, thereby facilitating the separation of cellulose molecules, resulting in cellulose dissolution; the hydroxide solution forms new hydrogen bonds with the cellulose at low temperature, and the urea hydrate wraps the hydroxide-hydrogen bond-cellulose to form inclusion compound, thereby dissolving the cellulose.
Dissolving cellulose in a system, obtaining a polymer film by a freeze drying method, rolling the polymer film, and soaking the rolled polymer film in a liquid electrolyte for a period of time to obtain a gel polymer electrolyte; or dissolving cellulose in a dissolving system, casting the cellulose on a substrate, placing the substrate on a heating plate to remove the solvent, drying the substrate in vacuum to obtain a compact nonporous polymer membrane, and soaking the membrane in an organic liquid electrolyte for a period of time to obtain a gel polymer electrolyte; or dissolving cellulose in a dissolving system, coating the solution on a substrate by a scraper, then placing the substrate on a heating plate to remove the solvent, then drying the substrate in vacuum to obtain a compact nonporous polymer film, and soaking the firm nonporous polymer film in an organic liquid electrolyte for a period of time to obtain a gel polymer electrolyte; or dissolving cellulose in an organic solvent, preparing a fibrous polymer film by an electrostatic spinning method, drying the fibrous polymer film, and soaking the fibrous polymer film in an organic liquid electrolyte for a period of time to obtain the gel polymer electrolyte.
The invention relates to a preparation method of natural cellulose gel polymer electrolyte, which has simple preparation process, low cost and environment-friendly preparation process. The prepared natural cellulose gel polymer electrolyte has high conductivity, wide electrochemical window, high ion migration number and good compatibility with electrode materials, can effectively inhibit the growth of metal dendrites, and obviously improves the cycle stability and rate capability of electrochemical energy storage devices such as batteries and the like. The gel polymer electrolyte can be used in a solid energy storage system with high energy density, large capacity, high power and high safety.
Drawings
FIG. 1 a is a scanning electron microscope image of the surface of a native cellulose membrane in example 1 of the present invention; b is the scanning electron microscope image of the surface of the glass fiber GF/A diaphragm of the comparative example 1.
FIG. 1 c is a scanning electron microscope image of a cross section of a native cellulose membrane according to example 1 of the present invention; d is the scanning electron microscope image of the surface of the glass fiber GF/A diaphragm of the comparative example 1.
FIG. 2 is a graph comparing the tensile force-stress curves of the natural cellulose film obtained in example 1 of the present invention and the GF/A glass fiber membrane used in comparative example 1.
FIG. 3 is a TG diagram of a natural cellulose membrane of an example of the present invention and a glass fiber GF/A membrane used in comparative example 1.
FIG. 4 shows 3mol L of natural cellulose gel polymer electrolyte obtained in example of the present invention and that obtained in comparative example 1-1ZnSO4The ionic conductivity of the glass fiber GF/A diaphragm of the electrolyte at different temperatures is compared with the Arrhenius equation curve.
FIG. 5 shows 3mol L of natural cellulose gel polymer electrolyte obtained in example of the present invention and that obtained in comparative example 1-1ZnSO4Comparative graph of zinc ion transference number test of glass fiber GF/A diaphragm of electrolyte.
Fig. 6-1 and 6-2 are electrochemical performances of Zn | natural cellulose gel polymer electrolyte | Zn and Zn | glass fiber-liquid electrolyte | Zn symmetric cells of example 1 of the present invention. FIG. 6-1 (a) is a graph of zinc ion deposition/dissolution voltage for two symmetric cells; detail drawings of 90-100 h; 990-1000 h of detail drawings; 1790-1800 h; FIG. 6-2 (b) is a SEM image of the surface of a fresh zinc electrode; fig. 6-2 (c) is an SEM image of the zinc electrode surface after 50 hours of cycling of the Zn | glass fiber-liquid electrolyte | Zn cell, and fig. 6-2 (d) is an SEM image of the zinc electrode surface after 800 hours of cycling of the Zn | gel polymer electrolyte | Zn cell.
FIG. 7 shows 3mol L of natural cellulose gel polymer electrolyte obtained in example of the present invention and that obtained in comparative example 1-1ZnSO4Circulation performance diagram (Zn/V) of glass fiber GF/A diaphragm of electrolyte2O5Battery, 2A g-1Current density).
FIG. 8 shows 3mol L of natural cellulose gel polymer electrolyte obtained in example of the present invention and that obtained in comparative example 1-1ZnSO4Multiplying power performance (Zn/V) of glass fiber GF/A diaphragm of electrolyte2O5A battery).
FIG. 9 shows a natural fiber according to an embodiment of the present inventionVitamin gel Polymer electrolyte and 0.5mol L obtained in comparative example 1-1(CH3COO)2Zn+CH3Cycle performance diagram of glass fiber GF/a membrane of COONa electrolyte (Zn/NVP @ rGO cell, 3C current density).
FIG. 10 shows 0.5mol L of a natural cellulose gel polymer electrolyte obtained in example of the present invention and that obtained in comparative example 1-1(CH3COO)2Zn+CH3Rate capability of glass fiber GF/A membrane of COONa electrolyte (Zn/NVP @ rGO battery).
In FIG. 11 a is Zn/V of example 1 of the present invention2O5Batteries at 2A g-1After 800 weeks of magnification cycling, the inhibition capacity of the natural cellulose gel polymer electrolyte for zinc dendrites was observed by SEM; b is Zn/V of comparative example 1 of the present invention2O5Batteries at 2A g-1After the magnification cycle for 200 weeks, the inhibition ability of the glass fiber GF/A membrane on zinc dendrites was observed by SEM.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
As shown in fig. 1 to 11
(1) 10g of anhydrous lithium chloride was added to 100mL of DMAc, and the mixture was stirred at 60 ℃ for 6 hours to obtain a clear solution.
(2) 5g of natural cellulose was added to the solution, and the mixture was stirred at 100 ℃ for 5 hours to obtain a pale yellow homogeneous solution.
(3) Pouring the dissolved solution onto a glass plate, drying on a heating plate at 60 ℃ for 5h, then putting into ultrapure water for soaking and washing, and finally putting into a vacuum drying oven at 60 ℃ for drying for 8h to obtain the cellulose membrane.
(4) Cutting the prepared electrolyte membrane into proper size, placing in a vacuum drying oven,dried at 80 ℃ for 24 hours to remove traces of water, cooled to room temperature under vacuum and transferred to a glove box for storage. Soaking in 3M ZnSO4And the natural cellulose polymer electrolyte is obtained after the electrolyte is added for 12 hours.
(5) Metal zinc as negative electrode, vanadium pentoxide (V)2O5) The anode and the natural cellulose gel polymer electrolyte are assembled into the aqueous zinc ion battery.
Example 2
(1) Reacting NMMO & H2The O is dissolved by heating at 110 ℃ until it is in a molten state. And then adding the natural cellulose raw material into the solution in a molten state to obtain a natural cellulose solution.
(2) The prepared natural cellulose solution was added to the injection solution and electrospun using a needle having a diameter of 0.3mm to prepare a natural cellulose fiber mesh membrane.
(3) The electrolyte membrane thus obtained was cut into a suitable size, placed in a vacuum drying oven, dried at 80 ℃ for 24 hours to remove the solution, cooled to room temperature under vacuum, and transferred into a glove box for storage. Immersing the polymer film in 2M ZnSO4And obtaining the natural cellulose hydrogel polymer electrolyte after the electrolyte is placed in the electrolyte for 12 hours.
(4) The metal zinc is used as a negative electrode, the commercially available activated carbon is used as a positive electrode, and the natural cellulose gel polymer electrolyte is assembled into the super capacitor.
Example 3
(1) An aqueous solution of NaOH/urea (7/12, wt%) was prepared and pre-cooled to-15 ℃, the natural cellulose raw material was added to the solution and stirred at 1500rpm for 5min to give a natural cellulose solution.
(2) Pouring the water solution into a storage container of a freeze dryer, and freeze-drying at the temperature of-60 ℃ and the vacuum degree of 10Pa in a cold trap.
(3) And (3) heating and rolling the dried product at 80 ℃ for 30 times to obtain a polymer film with the thickness of 35 mu m.
(4) Cutting the polymer film into proper size, drying in vacuum drying oven at 80 deg.C for 24 hr to remove trace water, cooling to room temperature under vacuum state, and rotatingTransferring into glove box for storage. Soaking in 0.5mol L-1(CH3COO)2Zn+CH3And (4) adding the COONa electrolyte for 12 hours to obtain the natural cellulose gel polymer electrolyte.
(5) The zinc ion battery is assembled by using metal zinc as a negative electrode, using sodium vanadium phosphate (NVP @ rGO) as a positive electrode and using natural cellulose gel polymer electrolyte.
Comparative example 1
Cutting a commercial zinc ion battery diaphragm glass fiber GF/A diaphragm into a proper size, then placing the battery diaphragm glass fiber GF/A diaphragm in a vacuum drying box at 80 ℃ for 24 hours, cooling the battery diaphragm glass fiber GF/A diaphragm under vacuum, and transferring the battery diaphragm glass fiber GF/A diaphragm into a glove box for storage. Before electrochemical test, the sample is soaked in 3M ZnSO4Electrolyte (purchased from yokkaiwa new materials co., ltd., yokkaido) for 12 hours.
The natural cellulose gel polymer film obtained by the method of the example 1 and the glass fiber GF/A diaphragm in the comparative example are characterized by infrared spectrum, scanning electron microscope, TG-DSC, liquid absorption rate, porosity and thermal shrinkage; TG-DSC, conductivity, lithium ion migration number, CV and charge and discharge tests are carried out on the natural cellulose-based gel polymer electrolyte and the glass fiber GF/A diaphragm absorbing the saturated liquid electrolyte.
Calculating the porosity, the prepared electrolyte membrane and a glass fiber GF/A diaphragm are soaked in n-butyl alcohol for 4 hours, and then the formula (1) is obtained:
wherein p is porosity, W0And WtRepresenting the mass of the film before and after the original sample and the saturated n-butanol, respectively. p and V are the density of n-butanol and the apparent volume of the membrane, respectively. The porosity of the polymer film obtained by the method of example 1 is 0.56%, and the porosity of the glass fiber GF/A diaphragm in the comparative example is 141.6%.
The liquid absorption rate of the prepared polymer film and the glass fiber GF/A diaphragm is calculated according to the formula (2) after two samples are soaked in the electrolyte for 12 hours:
η＝(Wt–W0)/W0×100％ (2)
wherein, W0And WtRespectively representing the quality of the original dry film and the film after fully absorbing the electrolyte. The liquid absorption rate of the polymer film obtained by the method of example 1 is 121.2%, and the liquid absorption rate of the glass fiber GF/A diaphragm in the comparative example is 519.6%.
The calculation of the conductivity is obtained according to equation (3):
σ＝l/(RbA)(S cm-1) (3)
where σ is the conductivity, l is the thickness of the film, RbAnd a is the resistance of the film and the area of the electrode, respectively. Example 1 method the room temperature conductivity of the natural cellulose based gel polymer electrolyte obtained by the method was 0.643mS cm-1The conductivity of the glass fiber GF/A diaphragm in the comparative example is 6.68mS cm-1。
The zinc ion transport number is calculated by the formula (4):
wherein, IoIs an initial current, IsIs a steady state current; roAnd RsCell resistances before and after polarization, respectively; Δ V is the step potential. The natural cellulose-based gel polymer electrolyte obtained by the method of example 1 has a zinc ion migration number of 0.46, and the glass fiber GF/A membrane of the comparative example has a zinc ion migration number of 0.3.
From the comparison between the examples and the comparative examples, the prepared natural cellulose-based gel polymer electrolyte has the characteristics of good thermal stability, low price, high safety at high temperature and the like, has good adhesion with the battery electrode, and can effectively prevent the micro short circuit of the battery. Compared with the traditional commercial diaphragm, the gel polymer electrolyte prepared by the embodiment has higher conductivity, zinc ion migration number and electrochemical property, and has important significance for the development of high-power and high-energy-density electric automobiles and large-scale energy storage equipment.
Claims (7)
1. The preparation method of the natural cellulose-based polymer electrolyte is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving natural cellulose in an NMMO system, a lithium halide/amide system, an ionic liquid, an alkaline water system, an alkali/urea system and other novel solvent systems to obtain a uniform natural cellulose solution;
(2) preparing a natural cellulose polymer film by casting, coating, papermaking, hot pressing, screen printing, freeze drying, electrostatic spinning, phase inversion, impregnation, foaming and Bellcore methods, wherein the thickness of the film is controlled to be 5-500 mu m;
(3) placing the natural cellulose polymer film obtained in the step (2) in a vacuum drying oven, drying at the temperature of room temperature to 300 ℃, and removing trace solvent;
(4) and (3) soaking the dried compound obtained in the step (3) in an electrolyte in an anhydrous and oxygen-free environment for 1 minute to 24 hours to obtain the natural cellulose polymer electrolyte.
2. The method for preparing a natural cellulose-based polymer electrolyte according to claim 1, wherein: the dissolving process of the step (1) is to stir and dissolve for 0.5 to 12 hours at the temperature of 100 ℃.
3. The method for preparing a natural cellulose-based polymer electrolyte according to claim 1, wherein: the electrolyte in the step (4) can be added into the natural cellulose solution in the step (1), and the natural cellulose membrane prepared by the method only needs to be soaked in the solvent of the electrolyte in the step (4).
4. The method for preparing a natural cellulose-based polymer electrolyte according to claim 1, wherein: the step (4) of preparing the natural cellulose gel polymer electrolyte is carried out at room temperature, and the electrolyte imbibing time is between 1min and 24 h.
5. The method for preparing a natural cellulose-based polymer electrolyte according to claim 1, wherein: the step (4) isThe electrolyte is composed of zinc salt, lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt and aluminum salt dissolved in carbonate, ether or pure water solvent or is ionic liquid with concentration of 0.1mol L-1-50mol L-1In the meantime.
6. The method for preparing a natural cellulose-based polymer electrolyte according to claim 1, wherein: the electrolyte adopted in the step (4) is zinc sulfate (ZnSO)4) Zinc acetate ((CH)3COO)2Zn), zinc trifluoromethanesulfonate (Zn (CF)3SO3)2) Zinc chloride (ZnCl), zinc nitrate (Zn (NO)3)2) Lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium bistrifluoromethanesulfonylimide (LiFSI), sodium perchlorate (NaClO4), lithium hexafluorophosphate (NaPF6), sodium bistrifluoromethanesulfonylimide (NaTFSI), sodium sulfate (Na)2SO4) Sodium acetate (CH)3COONa), sodium bis (fluorosulfonyl) imide (NaFSI), potassium perchlorate (KClO)4) Potassium hexafluorophosphate (KPF)6) Potassium tetrafluoroborate (KBF)4) Potassium hexafluoroarsenate (KAsF)6) Potassium bistrifluoromethanesulfonylimide (KTFSI), potassium bistrifluoromethylsulfonyl imide (KN (CF)3SO2)2) Calcium hexafluorophosphate (Ca (PF)6)2) Calcium chloride (CaCl)2) Calcium sulfate (CaSO)4) Calcium triflate ((CF)3SO3)2Ca), calcium perchlorate (Ca (ClO)4)2) Aluminum trifluoromethanesulfonate (Al (OTf)3) Aluminum chloride (AlCl)3) Aluminum nitrate (Al (NO)3)3) Aluminum sulfate (Al)2(SO4)3) One or more kinds of salt are mixed.
7. The method for preparing a natural cellulose-based polymer electrolyte according to claim 1, wherein: the electrolyte solvent adopted in the step (4) comprises carbonate, ether or pure water, such as one or more of ethylene carbonate, ethyl methyl carbonate, diethyl carbonate, propylene carbonate, vinylene carbonate, dimethyl carbonate, ethylene glycol diether, tetrahydrofuran, dioxolane and pure water.
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| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
| CN108063279A (en) * | 2016-11-07 | 2018-05-22 | 中国科学院化学研究所 | A kind of cellulose base gel polymer electrolyte and preparation method thereof and the lithium ion battery containing the electrolyte |
| CN110299557A (en) * | 2019-05-07 | 2019-10-01 | 南京工业大学 | Water soluble polymer gel polymer electrolyte and the preparation method and application thereof |
| CN113506951A (en) * | 2021-07-01 | 2021-10-15 | 丹阳欣信新材料科技有限公司 | Cellulose-based composite diaphragm for metal secondary battery and preparation method thereof |
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| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
| CN108063279A (en) * | 2016-11-07 | 2018-05-22 | 中国科学院化学研究所 | A kind of cellulose base gel polymer electrolyte and preparation method thereof and the lithium ion battery containing the electrolyte |
| CN110299557A (en) * | 2019-05-07 | 2019-10-01 | 南京工业大学 | Water soluble polymer gel polymer electrolyte and the preparation method and application thereof |
| CN113506951A (en) * | 2021-07-01 | 2021-10-15 | 丹阳欣信新材料科技有限公司 | Cellulose-based composite diaphragm for metal secondary battery and preparation method thereof |
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