CN105070870A - Preparation method and application of polymer-lignin composite material fibre membrane - Google Patents
Preparation method and application of polymer-lignin composite material fibre membrane Download PDFInfo
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- CN105070870A CN105070870A CN201510581383.0A CN201510581383A CN105070870A CN 105070870 A CN105070870 A CN 105070870A CN 201510581383 A CN201510581383 A CN 201510581383A CN 105070870 A CN105070870 A CN 105070870A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a preparation method and the application of a polymer-lignin composite material fibre membrane, and particularly relates to a lignin substrate-containing lithium-ion battery separation membrane and the preparation method thereof. The composite material fibre membrane is formed by compounding a polymer material and a lignin material, wherein the composite material fibre membrane comprises 30 to 90 mass percent of the polymer material and 10 to 70 mass percent of lignin material; the composite material fibre membrane is characterized in that the thickness of the composite material fibre membrane is 10 to 40 mu m, and the porosity is 40 to 80 percent; through hot pressing, the mechanical strength of the composite membrane is improved; the tensile strength is 20 to 60 MPa. According to the composite material fibre membrane, the advantages of high porosity and high liquid absorption rate of an electrostatic spinning separation membrane are maintained; meanwhile, the defect of poor mechanical property caused by the fact that an effective bonding point does not exist between the fibres in the electrostatic spinning separation membrane is overcome. When the separation membrane provided by the invention is applied to a lithium-ion battery, the electrochemical stability and the safety of the battery can be improved.
Description
Technical field
The present invention relates to a kind of polymer-lignin composite material tunica fibrosa, and the preparation method of this tunica fibrosa and the application in lithium ion battery thereof.
Background technology
Lithium ion battery grows up on the basis of secondary cell, it had both maintained the major advantage of lithium battery high voltage, high power capacity, there is again the distinguishing feature that security performance is good, have extended cycle life, have broad application prospects in portable electric appts, electric automobile, space technology, national defense industry etc., become the study hotspot widely paid close attention in recent years.。
Lithium ion battery is made up of positive and negative electrode, electrolyte and barrier film.As the core building block of lithium ion battery, the performance of barrier film determines the interfacial structure, internal resistance etc. of battery, the direct characteristic such as capacity, circulation and security performance affecting battery, the barrier film of excellent performance has important effect to the combination property improving battery.
Because traditional polyalkene diaphragm has good chemical stability, therefore in business-like lithium ion battery as main diaphragm application.But there is bad mechanical property (transverse direction), poor heat stability due to polyalkene diaphragm, the shortcomings such as porosity is low, wetability difference, thus limit the development of the lithium ion battery of high-energy-density.
Fabric nonwoven cloth prepared by electrostatic spinning technique has that size is little, even aperture distribution, porosity are high, be conducive to the advantages such as particulate penetrates, be made into lithium battery diaphragm, obstruct both positive and negative polarity can be played, prevent the object of short circuit, the ion between both positive and negative polarity can be allowed again to pass freely through, improve the cycle performance of battery, extend battery.
Summary of the invention
The object of this invention is to provide a kind of preparation method of lithium ion battery separator, this preparation method can make mutually to bond between fiber and fiber in barrier film, improves mechanical strength and does not affect the basic structure of tunica fibrosa, the performance of lithium ion battery is improved.
Polymer of the present invention-lignin composite material tunica fibrosa by method of electrostatic spinning and further hot pressing obtains, and described composite fiber film is made up of polymeric material and lignin material compound; Wherein: the mass percentage content of polymeric material in composite fiber film is 30-90%, the mass percentage content of lignin material in composite fiber film is 10-70%.
Described composite fiber film, its thickness is 20-40 μm, and porosity is 40-80%, and hot strength is 20-60MPa.
Described polymer-lignin composite material tunica fibrosa, is characterized in that: described polymeric material is selected from any one or the wherein blend of any two kinds in polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyethylene glycol oxide (PEO), polyether sulfone (PES), Kynoar (PVDF), Kynoar-hexafluoropropylene (PVDF-HFP) copolymer.
The mixture of any one or any two during described organic solvent is selected from DMF, DMA, acetone, tetrahydrochysene are barked and muttered.
The preparation method of polymer of the present invention-lignin composite material tunica fibrosa comprises the following steps:
1) preparation of composite spinning solution
Being dissolved in by polymeric material in organic solvent, is 40-60 in temperature.Obtain polymer solution after stirring at DEG C, wherein, in polymer solution, the mass concentration of polymeric material is 7-15%; Lignin material is joined in above-mentioned polymer solution under constantly stirring, obtains homogeneous solution;
2) polymer-lignin composite material tunica fibrosa is prepared
By step 1) the composite spinning solution prepared is placed in the priming device of electrospinning device; The spinning head be connected with described priming device by feedstock transportation pipeline is fixed, and is 10-25cm by the distance adjustment between described spinning head and receiving system, at temperature is 20-40 DEG C, carries out co-blended spinning; Wherein, spinning head described in co-blended spinning solution injects with the speed of 0.5-7ml/h under the effect of syringe pump, the DC high voltage electric field of 15-30kV is applied between the receiving system described in described spinning head and ground connection, co-blended spinning solution to split at the tip of described spinning head point and produces jet under the effect of electric field force, described receiving system obtains composite cellulosic membrane, drying, hot pressing, finally obtains described composite cellulosic membrane.
Described polymer-lignin composite material tunica fibrosa, is characterized in that: described polymeric material is selected from any one or the wherein blend of any two kinds in polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyethylene glycol oxide (PEO), polyether sulfone (PES), Kynoar (PVDF), Kynoar-hexafluoropropylene (PVDF-HFP) copolymer.
The mixture of any one or any two during described organic solvent is selected from DMF, DMA, acetone, tetrahydrochysene are barked and muttered.
The equipment of described electrostatic spinning is the electrostatic spinning apparatus of the many spinning heads of stainless steel of the electrostatic spinning apparatus of stainless steel list spinning head, the electrostatic spinning apparatus of the many spinning heads of stainless steel or warp-weft two-way; Described electrostatic spinning receiving system is one or more in aluminium foil, iron plate, iron net, copper mesh, iron roller, aluminum drum and non-woven material.
Vacuum drying chamber temperature in described drying steps is 50-120 DEG C, and drying time is 12-63h.
Pressure in described calendaring processes is 10-50MPa, and hot pressing temperature is 50-200 DEG C, and pressure duration is 0.01h-1h.
A kind of lithium ion battery, comprising:
Positive pole, negative pole, battery diaphragm and battery case;
Positive pole can adopt to be made containing cathode active material LiFePO 4 material;
The active material of negative pole can be graphite, hard carbon, soft carbon, lithium titanate, cobalt acid lithium, lithium nickelate, lithium manganese phosphate or its combination or lithium sheet;
Lithium salts in electrolyte can be lithium hexafluoro phosphate, LiBF4, di-oxalate lithium borate, oxalic acid two lithium fluoroborate, lithium perchlorate, sodium hexafluoro phosphate, the two sodium fluoborate of sodium tetrafluoroborate, two oxalic acid Boratex, oxalic acid, sodium perchlorate, two trifluoromethanesulfonimide tetraethyl ammonium salt, two trifluoromethanesulfonimide triethyl methyl ammonium salt, two trifluoromethanesulfonimide two spiro quaternary ammonium salt, two trifluoromethanesulfonimide lithium; Nonaqueous solvents in electrolyte can be ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, propyl propionate or its combination;
Described barrier film is the barrier film described in claim 1.
The present invention be adopt method of electrostatic spinning and further hot pressing to prepare the tunica fibrosa of polymer-lignin composite material.The composite fiber film thickness that method of electrostatic spinning obtains is even, and porosity is high, and the polymer obtained by electrostatic spinning-lignin composite material tunica fibrosa hot pressing, improves its mechanical strength, is a kind of lithium ion battery separator of excellent performance.
Accompanying drawing explanation
Fig. 1 is the electron micrograph of polyacrylonitrile in embodiment 1-lignin composite material tunica fibrosa;
Fig. 2 is the electron micrograph of polyacrylonitrile in embodiment 1-lignin composite material tunica fibrosa;
Fig. 3 is the load-deformation curve of above-mentioned two kinds of barrier films and Celgard2400 barrier film;
Fig. 4 is above-mentioned two kinds of barrier films and the high rate performance curve of lithium ion battery under different current density of Celgard2400 barrier film;
Fig. 5 be above-mentioned two kinds with the cycle performance curve of the lithium ion battery of Celgard2400 barrier film.
Embodiment
Provide specific embodiments of the invention below.These specific embodiments only for describing the present invention further, do not limit the claims of the present patent application.
Embodiment 1
1) preparation of composite spinning solution
0.72g polyacrylonitrile is dissolved in 5.28gN, in dinethylformamide, obtains uniform solution A after stirring 24h at temperature is 50 DEG C, wherein, the mass concentration of the polyacrylonitrile in solution A is 12%; 0.08g lignin is joined in above-mentioned solution A under constantly stirring, continues stirring until dissolution homogeneity, obtain composite spinning solution; In composite spinning solution, the quality of lignin is 10% of polyacrylonitrile and lignin gross mass.
2) polymer-lignin composite material tunica fibrosa is prepared
By step 1) polyacrylonitrile-lignin composite spinning solution of preparing is injected in the syringe with flat mouth syringe needle, and syringe needle connects high voltage source, is the metal receiving system of a ground connection at the other end of distance syringe 19cm.The injection speed regulating syringe pump is 2ml/h, and slow boosted voltage, to 23kv, carries out co-blended spinning at temperature is 25 DEG C.From syringe needle ejection rice solution drawing-off under high voltage electric field effect of syringe, be collected on the aluminium-foil paper of metal receiving system with the form of tunica fibrosa, gained nonwoven film is placed in vacuum drying chamber, dry 48h at 60 DEG C, after noresidue solvent in film, take out, obtain polyacrylonitrile-lignin composite cellulosic membrane.
The polyacrylonitrile of preparation-lignin composite cellulosic membrane is carried out hot-pressing processing, and wherein, pressure is 16MPa, and hot pressing temperature is 100 DEG C, and the time is 0.01h, takes out, obtains polyacrylonitrile-lignin composite cellulosic membrane.
3) assembling of battery and test
The positive active material of battery is LiFePO4, and negative pole is lithium sheet, and barrier film is the barrier film of above-mentioned preparation, and electrolyte is 1MLiPF
6volume ratio be the mixed liquor of EC and DMC of 1: 1.Above-mentioned positive plate and lithium sheet, barrier film and electrolyte are assembled into CR2430 button cell in the glove box being full of hydrogen.
Embodiment 2
The operating procedure of embodiment 2 is substantially identical with embodiment 1, and difference changes the quality of the lignin added in solution A into 0.31g, and in composite spinning solution, the quality of lignin is 30% of polyacrylonitrile and lignin gross mass, and other steps are with embodiment 1.
Comparative example 1
Adopt business-like polyalkene diaphragm Celgard2400 as a comparison, to illustrate the advantage of the composite fibre barrier film described in the present invention further.
Fig. 1 and Fig. 2 is the electron micrograph of the polyacrylonitrile-lignin composite material tunica fibrosa of different proportion.Can find out, along with increasing of content of lignin, fibre diameter increases, and diameter range is 200-800um.After hot pressing, be formed with effective adhesive point between fiber and there is three-dimensional net structure.Effectively can improve mechanical strength and the pick up of barrier film.
Fig. 2 is the load-deformation curve of above-mentioned three kinds of barrier films and Celgard2400 barrier film.Can find out, the ultimate tensile strength that above-mentioned three kinds of barrier films can bear is respectively 29.99 and 22.42MPa, and the horizontal ultimate tensile strength of Celgard2400 barrier film is 13.46MPa.The barrier film that hot strength is large is in use not easy the distortion that is stretched, and improves the security performance of battery.
Fig. 3 is above-mentioned two kinds of barrier films and the high rate performance curve of lithium ion battery under different current density of Celgard2400 barrier film.Charging/discharging voltage scope 2.0-4.2V.Can find out, the battery of the two kinds of barrier film assemblings using said method to prepare, test current density under, discharge capacity all higher than Celgard2400 barrier film, the composite cellulosic membrane especially in embodiment 2, under 0.2,0.5,1,2,4 and 8C, discharge capacity can reach 167.1 respectively, and 150.6,131.8,109.5,86.9and63.8mAh/g.
Fig. 4 is the cycle performance curve of lithium ion battery.Charging/discharging voltage scope 2.0-4.2V, current density 0.2C.The battery of the two kinds of barrier film assemblings using said method to prepare, stability test can be good, and after 50 circulations, capability retention is 95%, and performance is better than Celgard2400 barrier film.
Claims (9)
1. polymer-lignin composite material tunica fibrosa, its by method of electrostatic spinning and further hot pressing obtain; It is characterized in that: described composite fiber film is made up of polymeric material and lignin material compound; Wherein: the mass percentage content of polymeric material in composite fiber film is 30-90%, the mass percentage content of lignin material in composite fiber film is 10-70%;
Described composite fiber film, its thickness is 20-40 μm, and porosity is 40-80%, and hot strength is 20-60MPa.
2. polymer according to claim 1-lignin composite material tunica fibrosa, is characterized in that: described polymeric material is selected from any one or the wherein blend of any two kinds in polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyethylene glycol oxide (PEO), polyether sulfone (PES), Kynoar (PVDF), Kynoar-hexafluoropropylene (PVDF-HFP) copolymer.
3. a preparation method for the polymer according to claim 1-2 any one-lignin composite material tunica fibrosa, is characterized in that: the method comprises the following steps:
1) preparation of composite spinning solution
Be dissolved in by polymeric material in organic solvent, obtain polymer solution after stirring at temperature is 40-60 DEG C, wherein, in polymer solution, the mass concentration of polymeric material is 7-15%; Lignin material is joined in above-mentioned polymer solution under constantly stirring, obtains homogeneous solution;
2) polymer-lignin composite material tunica fibrosa is prepared
By step 1) the composite spinning solution prepared is placed in the priming device of electrospinning device; The spinning head be connected with described priming device by feedstock transportation pipeline is fixed, and is 10-25cm by the distance adjustment between described spinning head and receiving system, at temperature is 20-40 DEG C, carries out co-blended spinning; Wherein, spinning head described in co-blended spinning solution injects with the speed of 0.5-7ml/h under the effect of syringe pump, the DC high voltage electric field of 15-30kV is applied between the receiving system described in described spinning head and ground connection, co-blended spinning solution to split at the tip of described spinning head point and produces jet under the effect of electric field force, described receiving system obtains composite cellulosic membrane, drying, hot pressing, finally obtains described composite cellulosic membrane.
4. preparation method according to claim 3, is characterized in that: described polymeric material is selected from any one or the wherein blend of any two kinds in polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyethylene glycol oxide (PEO), polyether sulfone (PES), Kynoar (PVDF), Kynoar-hexafluoropropylene (PVDF-HFP) copolymer.
5. preparation method according to claim 3, is characterized in that: the mixture of any one or any two during described organic solvent is selected from DMF, DMA, acetone, tetrahydrochysene are barked and muttered.
6. preparation method according to claim 3, it is characterized in that, the equipment of described electrostatic spinning is the electrostatic spinning apparatus of the electrostatic spinning apparatus of stainless steel list spinning head, the electrostatic spinning apparatus of the many spinning heads of stainless steel or the many spinning heads of stainless steel of warp-weft two-way; Described electrostatic spinning receiving system is one or more in aluminium foil, iron plate, iron net, copper mesh, iron roller, aluminum drum and non-woven material.
7. preparation method according to claim 3, is characterized in that, the vacuum drying chamber temperature in described drying steps is 50-120 DEG C, and drying time is 12-63h.
8. preparation method according to claim 3, is characterized in that, the pressure in described heat-press step is 10-50Mpa, and hot pressing temperature is 50-200 DEG C, and pressure duration is 0.01h-1h.
9. a lithium ion battery, comprising: positive pole, negative pole, battery diaphragm and battery case; Described barrier film is the barrier film described in claim 1.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105568413A (en) * | 2015-12-22 | 2016-05-11 | 中国科学院山西煤炭化学研究所 | Lignin-based hollow fiber and preparation method thereof |
| CN106129310A (en) * | 2016-08-31 | 2016-11-16 | 合肥国轩高科动力能源有限公司 | Preparation method of lithium ion battery diaphragm |
| CN106757536A (en) * | 2016-12-12 | 2017-05-31 | 大连工业大学 | A kind of lignin-base activated carbon fiber of alkali activation and preparation method thereof |
| CN107331825A (en) * | 2017-07-13 | 2017-11-07 | 厦门大学 | A kind of preparation of high safety ceramic diaphragm and its application in lithium ion battery |
| CN107591531A (en) * | 2017-09-25 | 2018-01-16 | 华南师范大学 | A kind of lithium/sodium double ion manganese-base oxide positive electrode and preparation method and application |
| ES2712483A1 (en) * | 2017-11-13 | 2019-05-13 | Shengmin Li | An ultrafiltration membrane and its preparation procedure (Machine-translation by Google Translate, not legally binding) |
| KR20190059634A (en) * | 2017-11-23 | 2019-05-31 | 셩민 리 | An ultrafiltration membrane and its preparation method |
| KR20190074624A (en) * | 2017-12-20 | 2019-06-28 | 셩민 리 | An ultrafiltration membrane and its preparation method |
| CN110444719A (en) * | 2019-08-13 | 2019-11-12 | 四川轻化工大学 | High-strength composite lithium ion battery diaphragm |
| CN110943258A (en) * | 2019-12-16 | 2020-03-31 | 电子科技大学 | PVDF-HFP composite lignocellulose gel polymer electrolyte membrane and preparation method thereof |
| CN111933878A (en) * | 2020-07-06 | 2020-11-13 | 东莞市创明电池技术有限公司 | Lithium ion battery diaphragm and preparation method and application thereof |
| CN112397850A (en) * | 2020-11-12 | 2021-02-23 | 同济大学 | Modified lignocellulose diaphragm for lithium ion battery and preparation method and application thereof |
| CN113146911A (en) * | 2020-09-28 | 2021-07-23 | 蜂巢能源科技有限公司 | High-temperature-resistant diaphragm, dry preparation method and application thereof |
| CN114539554A (en) * | 2022-03-11 | 2022-05-27 | 东北师范大学 | Lignin-based single-ion polymer electrolyte, and preparation method and application thereof |
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| CN105568413A (en) * | 2015-12-22 | 2016-05-11 | 中国科学院山西煤炭化学研究所 | Lignin-based hollow fiber and preparation method thereof |
| CN106129310A (en) * | 2016-08-31 | 2016-11-16 | 合肥国轩高科动力能源有限公司 | Preparation method of lithium ion battery diaphragm |
| CN106757536A (en) * | 2016-12-12 | 2017-05-31 | 大连工业大学 | A kind of lignin-base activated carbon fiber of alkali activation and preparation method thereof |
| CN107331825A (en) * | 2017-07-13 | 2017-11-07 | 厦门大学 | A kind of preparation of high safety ceramic diaphragm and its application in lithium ion battery |
| CN107591531A (en) * | 2017-09-25 | 2018-01-16 | 华南师范大学 | A kind of lithium/sodium double ion manganese-base oxide positive electrode and preparation method and application |
| ES2712483A1 (en) * | 2017-11-13 | 2019-05-13 | Shengmin Li | An ultrafiltration membrane and its preparation procedure (Machine-translation by Google Translate, not legally binding) |
| KR20190059634A (en) * | 2017-11-23 | 2019-05-31 | 셩민 리 | An ultrafiltration membrane and its preparation method |
| KR102464154B1 (en) * | 2017-11-23 | 2022-11-07 | 셩민 리 | An ultrafiltration membrane and its preparation method |
| KR20190074624A (en) * | 2017-12-20 | 2019-06-28 | 셩민 리 | An ultrafiltration membrane and its preparation method |
| KR102473581B1 (en) | 2017-12-20 | 2022-12-02 | 셩민 리 | An ultrafiltration membrane and its preparation method |
| CN110444719A (en) * | 2019-08-13 | 2019-11-12 | 四川轻化工大学 | High-strength composite lithium ion battery diaphragm |
| CN110943258A (en) * | 2019-12-16 | 2020-03-31 | 电子科技大学 | PVDF-HFP composite lignocellulose gel polymer electrolyte membrane and preparation method thereof |
| CN111933878A (en) * | 2020-07-06 | 2020-11-13 | 东莞市创明电池技术有限公司 | Lithium ion battery diaphragm and preparation method and application thereof |
| CN113146911B (en) * | 2020-09-28 | 2022-06-17 | 蜂巢能源科技有限公司 | High-temperature-resistant diaphragm, dry preparation method and application thereof |
| CN113146911A (en) * | 2020-09-28 | 2021-07-23 | 蜂巢能源科技有限公司 | High-temperature-resistant diaphragm, dry preparation method and application thereof |
| CN112397850A (en) * | 2020-11-12 | 2021-02-23 | 同济大学 | Modified lignocellulose diaphragm for lithium ion battery and preparation method and application thereof |
| CN114539554A (en) * | 2022-03-11 | 2022-05-27 | 东北师范大学 | Lignin-based single-ion polymer electrolyte, and preparation method and application thereof |
| CN114539554B (en) * | 2022-03-11 | 2022-08-16 | 东北师范大学 | Lignin-based single-ion polymer electrolyte, and preparation method and application thereof |
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