CN108232085A - Poly ion liquid coated bacteria cellulose membrane and preparation method thereof - Google Patents
Poly ion liquid coated bacteria cellulose membrane and preparation method thereof Download PDFInfo
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- CN108232085A CN108232085A CN201711416949.XA CN201711416949A CN108232085A CN 108232085 A CN108232085 A CN 108232085A CN 201711416949 A CN201711416949 A CN 201711416949A CN 108232085 A CN108232085 A CN 108232085A
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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
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
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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
- 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
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of bacteria cellulose films and preparation method thereof, wherein, the surface of the nanofiber of the bacteria cellulose film is coated with a strata ionic liquid, combination of the poly ion liquid for one or more of imidazole salt, pyrrolidines salt, piperidines salt and quaternary ammonium salt poly ion liquid；Preparation method includes the following steps：Bacteria cellulose film is sequentially placed into poly ion liquid aqueous solution and impregnates 2h~48h, dipping 30min in precipitating reagent~for 24 hours, 2h~48h is impregnated in lithium salt solution, it is finally ironed using hot press, it is dry after to obtain the final product.The invention has the beneficial effects that：(1) poly ion liquid coated bacteria cellulose membrane has the advantages that high mechanical strength, thermal stability are good, lyophily is good, porosity is high and ionic conductivity is big, can improve cyclical stability and the safety of lithium ion battery；(2) preparation method is simple, and equipment requirement is low, is suitble to large-scale production.
Description
Technical field
The present invention relates to a kind of bacteria cellulose films and preparation method thereof, and in particular to it is a kind of by poly ion liquid cladding
Bacteria cellulose film and preparation method thereof belongs to electrochemical technology field.
Background technology
Diaphragm is the key building block of lithium ion battery, be influence lithium ion battery security, capacity, service life and
The key factor of the indexs such as cost.With the green of lithium ion battery, safety, long-life and high power density, there is an urgent need for
Develop High-performance diaphragm.
Traditional lithium ion battery separator due to the shortcomings of safety is low, efficiency for charge-discharge is low, service life is short, so
The performance requirement of novel power battery can not be met.Therefore, research and development high-performance novel power battery diaphragm, which has become, is
The important technical field of countries in the world competition.
At present, lithium ion battery separator in the market is mainly polyolefin porous membrane, this diaphragm by polyethylene (PE) and
Polypropylene (PP) is prepared for raw material, and preparation process is simple, and production efficiency is high, but equipment is complicated, has raised the system of diaphragm
Make cost.
In addition, it is crucial that, this diaphragm there are many shortcomings, such as：
1st, heat resistance is bad, and high temperature easily occurs to be heat-shrinked (PP melting temperatures are 165 DEG C), leads to battery security not
It is high；
2nd, porosity is low, causes imbibition rate low and is unfavorable for high current charge-discharge；
3rd, surface can be low, is unfavorable for and the combination of positive and negative plate, and interface resistance is big, influences the energy density of battery；
4th, hydrophily is bad, and the wetting and holding to electrolyte are inadequate, influence migration and the battery security of lithium ion.
These shortcomings cause polyolefin porous membrane to be difficult to the requirement for meeting novel power battery.
In recent years, high-performance power battery diaphragm is all competitively developed in European and American developed countries and area.Gathered using heat safe
Object (such as polyethylene terephthalate, polyimides, aromatic polyamide, polyparaphenylene's benzodiazole) is closed, passes through electrostatic
Spinning technique prepares nano fibrous membrane, can obtain that high porosity, heat resistance are high, lyophily is good, ionic conductivity is high, service life
Long lithium ion battery separator.The exploitation of German Degussa companies using polyethylene terephthalate diaphragm as substrate, ceramics
The composite membrane of grain coating, shows excellent heat resistance, closed pore temperature is up to 220 DEG C.The one of German EVONIC companies exploitation
Money dedicated for power battery High-performance diaphragmThe safe temperature of the film is up to 210 DEG C, percent thermal shrinkage
Less than 1% (200 DEG C, for 24 hours), wellability is obviously improved, and has outstanding thermal stability and chemical stability.Japanese Supreme Being people's technology
Products Co., Ltd developed the aramid nano-fiber that can be mass-produced in 2013, and the fiber size is uniform, had good
Heat-resisting and antioxygenic property, and in the form of non-woven sheet be applied to lithium ion battery separator manufacture.
Equally, lithium ion battery separator is prepared using heat-resistant polymer, cost of manufacture is higher, leads to lithium ion battery valency
Lattice drop is not got off.
Bacteria cellulose (BC) is the high purity cellulose synthesized under certain condition by bacterium, and molecular backbone is by grape
Glycan molecule is formed, and the nanofiber of high intensity is formed by strong hydrogen bonding, has a large amount of polar groups and the porous knot of three-dimensional micro-nano
Structure.Bacteria cellulose film is excellent with high porosity, high water retention, high-fire resistance, very good mechanical properties, good biocompatibility etc.
Point is applied in fields such as biomedicine, environmental protection, energy and materials, also has in terms of lithium ion battery separator extensive
Commercial applications prospect.Jiang Feng scapes et al. are prepared for ultra-thin bacteria cellulose film diaphragm using improved heat pressing process
(CN104157815B), this diaphragm (dry film) can use as lithium ion battery separator, but this ultra-thin bacterial fibers
Plain diaphragm porosity is relatively low, and the diaphragm so as to cause Conductivity Ratio business is low.Then, Jiang Fengjing et al. is further through in bacterial fibers
Coating inorganic nanoparticles obtain inorganic coating bacteria cellulose porous membrane (CN106450115A) on plain nanofiber, this
Kind diaphragm has the characteristics that elasticity modulus is high, lyophily is good, conductivity is high, thermal stability is good, can improve lithium ion battery dynamic
The performance of power battery, extensive energy storage etc. and safety.Model tinkling of pieces of jades et al. is made by dipping method (CN106531931A)
Bacteria cellulose film sucks nitrate and nano-oxide particles, is then decomposed nitrate with the method that substep hot pressing is dried
To metal oxide-cellulose composite membrane, during for lithium ion battery separator, battery shows excellent performance and safety,
But since silica dioxide granule is dispersed in the hole of bacteria cellulose film, the porosity of cellulose membrane can not be effectively increased,
It is likely to reduced the adsorbance of electrolyte instead, causes membrane properties that cannot embody very well.
During using bacteria cellulose film as lithium ion battery separator, hydroxyl meeting and lithium ion due to cellulose membrane surface
Coordinate, reduce the dissociation capability of lithium ion, ionic conductivity is caused to be lower；Also, for height of the lithium metal as electrode
During performance lithium ion battery, cellulose membrane surface reactive group may react with lithium metal, reduce the safety of battery
And Long Service Life.Therefore, it is necessary to handle bacteria cellulose film surface, while introduce and promote wanting for lithium ion transport
Element improves the ionic conductivity of cellulosic separator.
Invention content
The present invention first be designed to provide it is a kind of have higher porosity, imbibition rate and ionic conductivity and
The bacteria cellulose film of outstanding high temperature dimensional stability.
Second object of the present invention, which is to provide, a kind of to be simple and efficient, at low cost prepares above-mentioned bacteria cellulose film
Method.
In order to realize above-mentioned first aim, the present invention adopts the following technical scheme that：
A kind of bacteria cellulose film, which is characterized in that the surface of the nanofiber of aforementioned bacteria cellulose membrane is coated with one
Strata ionic liquid.
Aforementioned bacteria cellulose film, which is characterized in that aforementioned poly ion liquid is imidazole salt, pyrrolidines salt, piperazine
The combination of one or more of pyridine salt and quaternary ammonium salt poly ion liquid.
In order to realize above-mentioned second target, the present invention adopts the following technical scheme that：
The method for preparing aforementioned bacteria cellulose film, which is characterized in that include the following steps：
(1) bacteria cellulose film is placed in poly ion liquid aqueous solution, impregnates 2 hours~48 hours, make bacterial fibers
Plain film adsorbs poly ion liquid；
(2) bacteria cellulose film that step (1) obtains is put into precipitating reagent, impregnates 30 minutes~24 hours, gathered
The bacteria cellulose film of ionic liquid cladding；
(3) bacteria cellulose film that the poly ion liquid that step (2) obtains coats is put into lithium salt solution, dipping 2 is small
When~48 hours, it obtains exchanging the poly ion liquid coated bacteria cellulose membrane after anion；
(4) using hot press by step (3) obtain exchange anion after poly ion liquid coated bacteria cellulose membrane
It is ironed, it then dries, obtains clean poly ion liquid coated bacteria cellulose membrane.
Aforementioned method, which is characterized in that in step (1), a concentration of the 0.001% of aforementioned poly ion liquid aqueous solution
~5%.
Aforementioned method, which is characterized in that in step (2), aforementioned precipitating reagent is acetone, ethyl alcohol, methanol and isopropanol
In one or more mixing.
Aforementioned method, which is characterized in that in step (3), aforementioned lithium salts is perfluoro alkyl sulfonic acid lithium, perfluoroalkyl sulphur
One or more mixing in imide li, per-fluoroalkyl sulfonyl lithium methide and lithium hexafluoro phosphate, a concentration of 0.01%~
10%.
The invention has the beneficial effects that：
(1) poly ion liquid coated bacteria cellulose membrane
May be used as lithium ion battery separator, have high mechanical strength, thermal stability is good, lyophily is good, porosity is high and
The advantages of ionic conductivity is big can improve cyclical stability and the safety of lithium ion battery.
A strata ionic liquid is loaded in nanofiber surface, the combination of cellulose hydroxyl group and lithium ion can be overcome, and
And poly ion liquid can promote the dissociation of the corresponding anion of lithium ion, improve the conductivity of electrolyte lithium ion and quick
Transfer ability is suitable as the diaphragm of novel high-power power lithium-ion battery.
Poly ion liquid is loaded using cheap and abundance bacteria cellulose, cost of manufacture reduces, and then can reduce
Lithium ion battery price.
(2) preparation method
Preparation method is simple, and equipment requirement is low, is suitble to large-scale production.
Description of the drawings
Fig. 1 (a) is the micro-structure diagram of BC films；
Fig. 1 (b) is the micro-structure diagram of [email protected] films；
Fig. 2 is BC@PILs1 films figure compared with the electrochemical window of BC films；
Fig. 3 is the ionic conductivity of BC@PILs1 films and the relational graph of poly ion liquid solution concentration；
Fig. 4 is BC PILs1-1.0 films figure compared with the battery charging and discharging performance of BC films and commercialization PP films；
Fig. 5 is the micro-structure diagram of [email protected] films；
Fig. 6 is the ionic conductivity of BC@PILs2 films and the relational graph of poly ion liquid solution concentration；
Fig. 7 is the micro-structure diagram of [email protected] films；
Fig. 8 is the ionic conductivity of BC@PILs3 films and the relational graph of poly ion liquid solution concentration；
Fig. 9 is the micro-structure diagram of [email protected] films；
Figure 10 is the ionic conductivity of BC@PILs4 films and the relational graph of poly ion liquid solution concentration.
Specific embodiment
Above-mentioned technical proposal to enable the present invention is more obvious understandable, in the following with reference to the drawings and specific embodiments to this
Detailed introduction is done in invention.
Embodiment 1
The polydiallyldimethyl aqueous ammonium chloride solution (poly ion liquid aqueous solution) of 100mL a concentration of 1.0% is prepared, 4g
Bacteria cellulose film (wet film), which is placed in the solution, to be impregnated 24 hours, is slowly stirred and (is conducive to the expansion of polydiallyldimethyl ammonium chloride
It is scattered in bacteria cellulose film), surface slightly is cleaned with deionized water after taking-up, is subsequently placed in 50mL acetone (precipitating reagent) and soaks
Bubble 12 hours makes polydiallyldimethyl ammonium chloride precipitation completely be coated on nanofiber surface, it is a concentration of to be placed in 50mL again later
It is impregnated 24 hours in 0.5% double trifluoromethanesulfonimide lithium ethanol solutions, is slowly stirred and (is conducive to double fluoroform sulphonyl
Imines ion is swapped with chlorion), it is finally in 60 DEG C that wet film is ironed using hot press and 24 hours dry at 80 DEG C,
Up to poly ion liquid coated bacteria cellulose membrane, it is denoted as [email protected] films.
The main chemical compositions of [email protected] films are bacteria cellulose and quaternary ammonium salt poly ion liquid.
The microstructure of [email protected] films that the present invention is prepared is shown in Fig. 1 (b), and [email protected] films have three
Tie up micro-nano porous structure.
The microstructure of pure bacteria cellulose film (BC films) is shown in Fig. 1 (a).
Comparison diagram 1 (a) and Fig. 1 (b) are it is found that poly ion liquid coats and is not apparent from increasing the Nanowire of bacteria cellulose film
The diameter of dimension, and it is little to the Porosity Rate Influence of bacteria cellulose film, it can still keep high imbibition rate.
Diaphragm (BC@PILs1 films, BC films) and lithium piece, stainless steel substrates (SS) have been assembled into Li/ diaphragms/SS structures by us,
And the electrochemical stability of the structure is tested, test result is shown in Fig. 2.
As shown in Figure 2, the electrochemical window of BC films is about 4.6V, the electrochemical windows of BC@PILs1 films reach 4.8V with
On, BC@PILs1 films have higher electrochemical window than BC film, and load poly ion liquid can reduce cellulose surface hydroxyl
With the effect of lithium metal, the electrochemical stability of bacteria cellulose film is improved.
Between diaphragm (BC@PILs1 films, commercialization PP films) is sandwiched in stainless steel substrates (SS) by us, be assembled into SS/ diaphragms/
SS structures, and the ionic conductivity of the structure is tested, test result is shown in Fig. 3.
From the figure 3, it may be seen that BC@PILs1 films than commercialization PP films have higher ionic conductivity, fiber surface cladding gather from
Sub- liquid improves the ionic conductivity of commercialization PP films.
We are by diaphragm ([email protected] films, commercialization PP films, BC films) and lithium piece, LiFePO4 (LiFePO4) group
Li/ diaphragms/LiFePO is dressed up4Structure, specific capacity and big high rate performance to the structure are tested, and test result is shown in figure
4。
As shown in Figure 4, using the battery of poly ion liquid coated bacteria cellulose membrane, battery capacity and high magnification charge and discharge
Electrical property significantly improves, and is superior to BC films and commercialization PP films.
Embodiment 2
Poly- [3- ethyl -1- vinyl imidazoles bromide] aqueous solution of 50mL a concentration of 0.05% is prepared, 2g bacterial fibers
Plain film (wet film), which is placed in the solution, impregnates 12 hours, is slowly stirred, slightly cleans surface with deionized water after taking-up, then put
It is impregnated 24 hours in 30mL ethyl alcohol, poly- [3- ethyl -1- vinyl imidazoles bromide] precipitation completely is made to be coated on Nanowire dimension table
Face is placed in the trifluoromethanesulfonic acid lithium ethanol solution of 40mL a concentration of 1.0% and impregnates 12 hours, is slowly stirred, finally again later
It is in 70 DEG C that wet film is ironed using hot press, and 60 DEG C dry 24 hours to get poly ion liquid coated bacteria cellulose membrane,
[email protected] films are denoted as, pattern is shown in Fig. 5.
The main chemical compositions of [email protected] films are bacteria cellulose and imidazole salt poly ion liquid.
The ionic conductivity of BC@PILs2 films is shown in Fig. 6.
It will be appreciated from fig. 6 that the performance of the BC@PILs2 films is substantially suitable with the performance of the BC@PILs1 films in embodiment 1.
Embodiment 3
Poly- [1- (4- the benzyls) -3- butylimidazoliums tetrafluoroborate] aqueous solution of 200mL a concentration of 2.0% is prepared,
8g bacterial cellulose wet-coatings, which are placed in the solution, to be impregnated 48 hours, is slowly stirred, slightly surface is cleaned with deionized water after taking-up,
It is subsequently placed in 100mL methanol and impregnates 24 hours, poly- [1- (4- benzyls) -3- butylimidazoliums tetrafluoroborate] is made to precipitate completely
Nanofiber surface is coated on, is placed in three (trimethyl fluoride sulfonyl) lithium methide ethanol solutions of 100mL a concentration of 5.0% again later
It is middle to impregnate 24 hours, be slowly stirred, it is finally in 60 DEG C that wet film is ironed using hot press, and 70 DEG C dry 24 hours to get
Poly ion liquid coated bacteria cellulose membrane, is denoted as [email protected] films, and pattern is shown in Fig. 7.
The main chemical compositions of [email protected] films are bacteria cellulose and imidazole salt poly ion liquid.
The ionic conductivity of BC@PILs3 films is shown in Fig. 8.
As shown in Figure 8, the performance of the BC@PILs3 films is substantially suitable with the performance of the BC@PILs1 films in embodiment 1.
Embodiment 4
The polymethyl acyloxyethyl trimethyl tetrafluoro boric acid aqueous ammonium of 150mL a concentration of 0.2% is prepared, 5g is thin
Fungin wet film, which is placed in the solution, to be impregnated 36 hours, is slowly stirred, is slightly cleaned surface with deionized water after taking-up, then
It is placed in 70mL methanol and impregnates 12 hours, be coated on polymethyl acyloxyethyl trimethyl ammonium tetrafluoroborate precipitation completely and receive
Rice fiber surface, is placed in the lithium hexafluoro phosphate ethanol solution of 80mL a concentration of 0.05% and impregnates 12 hours, slowly stir again later
It mixes, it is finally in 70 DEG C that wet film is ironed using hot press, and 24 hours are dried to get poly ion liquid coated bacteria fibre at 80 DEG C
The plain film of dimension, is denoted as [email protected] films, pattern is shown in Fig. 9.
The main chemical compositions of [email protected] films are bacteria cellulose and quaternary ammonium salt poly ion liquid.
The ionic conductivity of BC@PILs4 films is shown in Figure 10.
As shown in Figure 10, the performance of the BC@PILs4 films is substantially suitable with the performance of the BC@PILs1 films in embodiment 1.
It should be noted that the invention is not limited in any way for above-described embodiment, it is all to use equivalent replacement or equivalent change
The technical solution that the mode changed is obtained, all falls in protection scope of the present invention.
Claims (7)
1. a kind of bacteria cellulose film, which is characterized in that the surface of the nanofiber of the bacteria cellulose film is coated with one layer
Poly ion liquid.
2. bacteria cellulose film according to claim 1, which is characterized in that the poly ion liquid is imidazole salt, pyrrole
Cough up the combination of one or more of alkane salt, piperidines salt and quaternary ammonium salt poly ion liquid.
3. prepare the method for bacteria cellulose film described in claim 1, which is characterized in that include the following steps：
(1) bacteria cellulose film is placed in poly ion liquid aqueous solution, impregnates 2 hours~48 hours, make bacteria cellulose film
Adsorb poly ion liquid；
(2) bacteria cellulose film that step (1) obtains is put into precipitating reagent, impregnates 30 minutes~24 hours, obtain polyion
The bacteria cellulose film of liquid cladding；
(3) bacteria cellulose film that poly ion liquid that step (2) obtains coats is put into lithium salt solution, dipping 2 hours~
It 48 hours, obtains exchanging the poly ion liquid coated bacteria cellulose membrane after anion；
(4) using hot press by step (3) obtain exchange anion after poly ion liquid coated bacteria cellulose membrane it is ironed,
Then it dries, obtains clean poly ion liquid coated bacteria cellulose membrane.
4. according to the method described in claim 3, it is characterized in that, in step (1), the poly ion liquid aqueous solution it is dense
Spend is 0.001%~5%.
5. according to the method described in claim 3, it is characterized in that, in step (2), the precipitating reagent is acetone, ethyl alcohol, first
One or more mixing in alcohol and isopropanol.
6. according to the method described in claim 3, it is characterized in that, in step (3), the lithium salts is perfluoro alkyl sulfonic acid
One or more mixing in lithium, per-fluoroalkyl sulfonyl imine lithium, per-fluoroalkyl sulfonyl lithium methide and lithium hexafluoro phosphate.
7. according to the method described in claim 6, it is characterized in that, a concentration of the 0.01%~10% of the lithium salts.
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| CN109950453A (en) * | 2019-03-25 | 2019-06-28 | 佛山市东航光电科技股份有限公司 | The bacteria cellulose film and preparation method thereof coated by poly-dopamine |
| CN110600739A (en) * | 2019-08-22 | 2019-12-20 | 浙江工业大学 | Preparation method of metal lithium negative electrode protection layer material |
| CN111584841A (en) * | 2020-05-15 | 2020-08-25 | 宁波锋成纳米科技有限公司 | Composite material, preparation method thereof and water-based lithium ion battery |
| CN112242553A (en) * | 2019-07-18 | 2021-01-19 | 北京理工大学 | Solid-state composite electrolyte and preparation method thereof |
| CN113270686A (en) * | 2021-05-25 | 2021-08-17 | 哈尔滨工业大学 | Preparation method of bacterial cellulose-based water-based zinc ion battery diaphragm material |
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| CN109280088B (en) * | 2018-09-11 | 2020-11-27 | 陕西科技大学 | Imidazole ionic liquid modified bacterial cellulose antibacterial film and preparation method thereof |
| CN109950453A (en) * | 2019-03-25 | 2019-06-28 | 佛山市东航光电科技股份有限公司 | The bacteria cellulose film and preparation method thereof coated by poly-dopamine |
| CN112242553A (en) * | 2019-07-18 | 2021-01-19 | 北京理工大学 | Solid-state composite electrolyte and preparation method thereof |
| CN112242553B (en) * | 2019-07-18 | 2024-03-19 | 北京理工大学 | Solid-state composite electrolyte and preparation method thereof |
| CN110600739A (en) * | 2019-08-22 | 2019-12-20 | 浙江工业大学 | Preparation method of metal lithium negative electrode protection layer material |
| CN111584841A (en) * | 2020-05-15 | 2020-08-25 | 宁波锋成纳米科技有限公司 | Composite material, preparation method thereof and water-based lithium ion battery |
| CN111584841B (en) * | 2020-05-15 | 2021-07-27 | 宁波锋成纳米科技有限公司 | Composite material, preparation method thereof and water-based lithium ion battery |
| CN113270686A (en) * | 2021-05-25 | 2021-08-17 | 哈尔滨工业大学 | Preparation method of bacterial cellulose-based water-based zinc ion battery diaphragm material |
| CN113270686B (en) * | 2021-05-25 | 2023-01-31 | 哈尔滨工业大学 | Preparation method of bacterial cellulose-based water-based zinc ion battery diaphragm material |
| CN113451709A (en) * | 2021-06-21 | 2021-09-28 | 云南大学 | Preparation method of cationized mushroom ion-conducting membrane and application of cationized mushroom ion-conducting membrane in lithium ion battery |
| CN113451709B (en) * | 2021-06-21 | 2022-08-09 | 云南大学 | Preparation method of cationized mushroom ion-conducting membrane and application of cationized mushroom ion-conducting membrane in lithium ion battery |
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