CN106601990A - Battery positive electrode based on nitrogen-doped carbonized bacterial cellulose, lithium-sulfur battery and preparation methods therefor - Google Patents
Battery positive electrode based on nitrogen-doped carbonized bacterial cellulose, lithium-sulfur battery and preparation methods therefor Download PDFInfo
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Abstract
The invention discloses a battery positive electrode based on nitrogen-doped carbonized bacterial cellulose, a lithium-sulfur battery and preparation methods therefor. An N source required in a bacterial cellulose biological culture process is adopted for N doping to prepare a battery positive electrode material; a battery sandwich layer with strong adsorption capacity is prepared by compounding of a super-light carbonized bacterial cellulose sandwich layer and porous carbon; a battery diaphragm material is prepared by combination of an ion selectivity barrier layer Nafion and bacterial cellulose aerogel; and the battery positive electrode based on the nitrogen-doped carbonized bacterial cellulose, the carbonized bacterial cellulose functional sandwich layer, and the Nafion/BC diaphragm are assembled into the lithium-sulfur battery. By virtue of the N element doping, the functional sandwich layer introducing and joint use of the Nafion/BC diaphragm, the dispersion of polysulfide to a lithium negative electrode is controlled in a multi-dimension manner, so that multi-level suppression specific to the dispersion of polysulfide is realized, and a shuttle effect is effectively controlled; and the assembled Li-S battery has high specific capacity, high coulombic efficiency and stable cycle performance.
Description
Technical field
The invention belongs to lithium-sulfur cell field, is related to a kind of anode, the lithium sulphur of the carbonization bacteria cellulose that adulterates based on N
Battery and preparation method thereof.
Background technology
Lithium ion battery is the best secondary cell of current combination property, in being widely used to all kinds of portable sets.
It is close to lithium ion battery energy with the fast development of the high energy consumption equipment facility such as electric automobile, intelligent grid and Aero-Space
The requirement also more and more higher of degree and power density.However, traditional lithium rechargeable battery is due to by the theoretical storage lithium of positive electrode
The restriction of capacity, it is difficult to make a breakthrough in terms of energy density is lifted, such as the most widely used LiCoO2Positive pole material
Expect that its theoretical energy density is only 387Wh kg-1, also far from meeting above-mentioned high energy consumption demand.Therefore, find new positive pole to live
Property material is particularly important.With simple substance S as positive pole, lithium metal is close by the theoretical energy that the Li-S batteries that negative pole is constituted have
Degree is up to 2567Wh kg-1(theoretical specific capacity 1675mAh g-1), far above the lithium ion battery of current commercialization.Additionally, single
Matter S also has the advantages that rich reserves, environmental friendliness, cheap and easy to get, so, lithium sulphur (Li-S) secondary cell enjoys the pass of people
Note.But Li-S batteries yet suffer from many problems to be needed to solve, mainly include that polysulfide dissolves produced in the electrolytic solution
" shuttle effect ", and during charge/discharge due to active material Volume Changes caused by electrode structure destruction, finally
All it is likely to result in that battery capacity is relatively low, coulombic efficiency is not high, cycle performance is poor.
It is well known that biological material aboundresources, wide material sources are cheap and easy to get, and are mostly reproducible environment
Friendly material, biomass carbon is by this class material char-forming material that under an inert atmosphere Jing high annealings are processed.It is biological
Matter material with carbon element can generally retain microstructure specific to its presoma, and be relatively easy to realize industrialized production.Bacterium
Cellulose (BC) is a kind of one dimension fibre element base large biological molecule synthesized by acetobacter xylinum metabolism, compared to plant cellulose,
It has great advantage at aspects such as purity, the degree of polymerization, degree of crystallinity and orientations.Carbonized product (the carbonization bacterium of biomass BC
Cellulose, CBC) there is unique three-dimensional netted macroporous structure, good pliability and mechanical stability.But as unformed
Material with carbon element, CBC shows relatively limited electronic conduction ability.Wang et al. (Bin Wang et al.Small, 2013,9
(14):Ge/CBC composites 2399-2404.) are prepared first for lithium ion battery, and the battery shows poor forthright again
Can, think that electrical conductivity is the key factor for affecting its battery performance.Additionally, high temperature cabonization obtain CBC apertures content compared with
It is low, therefore (the Yang Huang et relatively limited to dissolubility polysulfide absorption and control ability in Li-S battery operations
al.Journal of Materials Chemistry A,2015,3:10910-10918.).How answering based on CBC is improved
The electrical conductivity of condensation material, and it is that at present further optimization is based on CBC to efficiently control the diffusion of polysulfide in Li-S batteries
The key issue of Li-S batteries.
The content of the invention
An object of the present invention is to provide a kind of anode of the bacteria cellulose that is carbonized based on N doping.
Realize that the technical scheme of above-mentioned purpose is as follows：
A kind of anode of the bacteria cellulose that is carbonized based on N doping, is prepared by following steps：
Step 1, after bacteria cellulose diaphragm is taken out from culture medium, the unnecessary zymotic fluid on membrane removal surface is removed in washing, cold
Jelly is dried to obtain the bacteria cellulose aeroge containing nitrogen source；
Step 2, the bacteria cellulose aeroge pressing containing nitrogen source is processed, then under an inert atmosphere in 800-1000 DEG C
Lower carbonization, obtains N doping carbonization bacteria cellulose (NCBC) aeroge；
Step 3, by NCBC aeroges S/CS is impregnated in2In solution, after taking-up, carry out at 130-300 DEG C under closed environment
Heat treatment, makes simple substance S in molten condition, and equably diffuses to inside NCBC mesh, obtains being carbonized based on N doping after cooling
The amount containing S of the anode of bacteria cellulose, i.e. S/NCBC positive poles, wherein S/NCBC anode electrodes piece is 75-90wt%.
In step 1, the thickness of described bacteria cellulose diaphragm is 1.5-3.0mm.
In step 2, the pressure that described pressing is processed is 0.2Mpa, and described carbonization time is 1-3h.
In step 3, described dip time is 2-12h, and described heat treatment time is 6-24h.
Further, the present invention also provides a kind of anode material using the above-mentioned bacteria cellulose that is carbonized based on N doping
The Li-S batteries of material assembling, are prepared by following steps：
Step 1, after bacteria cellulose diaphragm is taken out from culture medium, with the NaOH boilings of 1M, washing is until cleaning solution
In neutrality, freeze-drying obtains pure bacteria cellulose aeroge, afterwards processes the pressing of bacteria cellulose aeroge, then
In 800-1000 DEG C of carbonization under inert atmosphere, ultralight carbonization bacteria cellulose (CBC) film is obtained；
Step 2, porous carbon is dispersed in 1-METHYLPYRROLIDONE, by the method for film by porous carbon dispersion liquid
Ultralight CBC films surface is compound to, the compound quantity of porous carbon is 0.10-0.20mg/cm2, as CBC function interlayers；
Step 3, pure BC aeroges are dipped in Nafion solution, fully are transferred in 1M LiOH solution after immersion
Row lithiumation process, temperature is kept for 60-100 DEG C, and pressing after freeze-drying is processed, as Nafion/BC barrier films, Nafion in barrier film
Compound quantity in pure BC aeroges is 0.2-1.0mg cm-2；
Step 4, with sulfonic acid imide li (LiTFSI) electrolyte of bis trifluoromethyl containing 1M, the lithium nitrate of 1.0wt% concentration
(LiNO3) additive, it is 1 that solvent is volume ratio:1 glycol dimethyl ether (DME) and the mixing of 1,3- dioxolanes (DOL) are molten
Liquid, used as electrolyte, with S/NCBC composites as positive pole, lithium metal is negative pole, and Nafion/BC barrier films are battery diaphragm, CBC
Function interlayer is placed between positive pole and barrier film and is assembled into Li-S batteries.
In step 1, the thickness of described bacteria cellulose diaphragm is 0.5-1.5mm.
In step 3, the area density of described pure BC aeroges is 0.5-3.0mg cm-2, the lithiumation time is 14h, described
Pressing process pressure be 0.2Mpa.
Compared with prior art, the present invention has following remarkable result：
The present invention carries out N doping and realizes atom economy using the N sources of biosynthesis itself, with macroreticular structure
NCBC as cell positive material carrier, significantly improve the load capacity of active material S, effectively buffering S bodies in charge/discharge
Product change.The N blended positive pole materials of the present invention can effectively improve the electrical conductivity of carbon carrier, and can control the expansion of polysulfide
Dissipate.Introduced by N element doping, function interlayer, Nafion/BC barrier films are used in combination, stage construction controls polysulfide to lithium
Negative pole spreads, and realizes the multistage suppression for polysulfide diffusion, effective control shuttle effect.The Li-S batteries tool that assembling is formed
There are height ratio capacity, high coulomb efficiency and stable cycle performance.
Description of the drawings
Fig. 1 is the lithium-sulfur cell modular construction schematic diagram of the present invention.
Fig. 2 is to spread multistage inhibitory action schematic diagram for polysulfide in battery operation.
Specific embodiment
Below by embodiment and accompanying drawing, the invention will be further described.
The porous carbon utilized in following examples and comparative example is commercialization porous carbon CMK-3, and simple substance S used is distillation
S, the electrolyte of the sulfonic acid of bis trifluoromethyl containing 1M imide li (LiTFSI), the lithium nitrate of 1wt% in the electrolyte of used in battery
(LiNO3) additive, it is 1 that solvent is volume ratio:1 glycol dimethyl ether (DME) and the mixing of 1,3- dioxolanes (DOL) are molten
Liquid.Lithium metal is used as GND.Battery diaphragm is Nafion/BC, and battery model used is CR2032 button cells.
Embodiment 1
A kind of preparation method of the anode based on N doping carbonization bacteria celluloses, comprises the following steps that：
Step 1, deionized water flushing membrane excess surface is sent out after thickness is taken out for the BC diaphragms of 3.0mm from culture medium
Zymotic fluid, then freeze-drying obtains the BC aeroges of source containing N.
Step 2, will contain N sources BC aeroges do pressing process (0.2Mpa normal pressures), then under inert atmosphere protection in
800 DEG C of insulation 2h, obtain NCBC aeroges.
Step 3, by NCBC aeroges infiltration to S/CS2In solution, 2h is stored at room temperature, is put into after taking-up in closed container,
6h is kept at a temperature of 130 DEG C, simple substance S is made in molten condition, and is equably diffused to inside NCBC mesh, obtained final product after cooling
S/NCBC positive poles, prepared S/NCBC positive electrodes amount containing S is 75wt%.
A kind of Li-S batteries using the above-mentioned cell positive material assembling based on N doping carbonization bacteria celluloses：
Step 1, with the NaOH boilings of 1M after thickness is taken out for the BC diaphragms of 0.5mm from culture medium, then uses deionization
Water is rinsed up to cleaning solution in neutrality repeatedly, and freeze-drying afterwards obtains pure BC aeroges, after processing the pressing of BC aeroges,
Under an inert atmosphere in 800 DEG C of carbonization treatments 1h, ultralight CBC films are obtained.
Step 2, the porous carbon CMK-3 being scattered in 1-METHYLPYRROLIDONE is uniformly compound to gently by the method for film
Matter CBC film surface, CMK-3 compound quantities are 0.10mg/cm2, composite is used as into Li-S battery functi on interlayers.
Step 3, is 0.5mg cm by area density-2Pure BC aeroges be dipped in Nafion solution, Nafion is in BC
Middle compound quantity is 0.2mg cm-2, being fully transferred in 1M LiOH solution after immersion carries out lithiumation process, 60 DEG C of temperature holding, when
Between maintain 14h, freeze-drying afterwards, with the pressure of 0.2Mpa do pressing process, make as Li-S battery Nafion/BC barrier films
With.
Step 4, by the use of S/NCBC composites, to do positive pole, lithium metal be negative pole, Nafion/BC used as battery diaphragm, CBC
Function interlayer is placed in assembled battery between positive pole and barrier film, the electrolyte containing 1M LiTFSI in used in battery electrolyte,
The LiNO of 1.0wt% concentration3Additive, it is 1 that solvent is volume ratio:The mixed solution of 1 DME and DOL.
Embodiment 2
A kind of preparation method of the anode based on N doping carbonization bacteria celluloses, comprises the following steps that：
Step 1, deionized water flushing membrane excess surface is sent out after thickness is taken out for the BC diaphragms of 2.0mm from culture medium
Zymotic fluid, then freeze-drying obtains the BC aeroges of source containing N.
Step 2, will contain N sources BC aeroges do pressing process (0.2Mpa normal pressures), then under inert atmosphere protection in
900 DEG C of insulation 1h, obtain NCBC aeroges.
Step 3, by NCBC aeroges infiltration to S/CS2In solution, 4h is stored at room temperature, is put into after taking-up in closed container,
10h is kept at a temperature of 200 DEG C, simple substance S is made in molten condition, and is equably diffused to inside NCBC mesh, after cooling i.e.
S/NCBC positive poles are obtained, prepared S/NCBC positive electrodes amount containing S is 80wt%.
A kind of Li-S batteries using the above-mentioned cell positive material assembling based on N doping carbonization bacteria celluloses：
Step 1, with the NaOH boilings of 1M after thickness is taken out for the BC diaphragms of 1.0mm from culture medium, then uses deionization
Water is rinsed up to cleaning solution in neutrality repeatedly, and freeze-drying afterwards obtains pure BC aeroges, right, after the pressing of BC aeroges is processed
Under an inert atmosphere in 900 DEG C of carbonization treatments 1h, ultralight CBC films are obtained.
Step 2, will be scattered in porous carbon CMK-3 in 1-METHYLPYRROLIDONE and is uniformly compound to lightweight by the method for film
CBC films surface.CMK-3 compound quantities are 0.17mg/cm2.The composite is used as into Li-S battery functi on interlayers.
Step 3, is 2.5mg cm by area density-2Pure BC aeroges be dipped in Nafion solution, Nafion is in BC
Middle compound quantity is 0.8mg cm-2, being fully transferred in 1M LiOH solution after immersion carries out lithiumation process, 90 DEG C of temperature holding, when
Between maintain 14h, freeze-drying afterwards, with the pressure of 0.2Mpa do pressing process, make as Li-S battery Nafion/BC barrier films
With.
Step 4, by the use of S/NCBC composites, to do positive pole, lithium metal be negative pole, Nafion/BC used as battery diaphragm, CBC
Function interlayer is placed in assembled battery between positive pole and barrier film.Electrolyte containing 1M LiTFSI in used in battery electrolyte,
The LiNO of 1.0wt% concentration3Additive, it is 1 that solvent is volume ratio:The mixed solution of 1 DME and DOL.
Embodiment 3
A kind of preparation method of the anode based on N doping carbonization bacteria celluloses, comprises the following steps that：
Step 1, deionized water flushing membrane excess surface is sent out after thickness is taken out for the BC diaphragms of 2.0mm from culture medium
Zymotic fluid, then freeze-drying obtains the BC aeroges of source containing N.
Step 2, will contain N sources BC aeroges do pressing process (0.2Mpa normal pressures), then under inert atmosphere protection in
1000 DEG C of insulation 1h, obtain NCBC aeroges.
Step 3, by NCBC aeroges infiltration to S/CS2In solution, 6h is stored at room temperature, is put into after taking-up in closed container,
12h is kept at a temperature of 160 DEG C, simple substance S is made in molten condition, and is equably diffused to inside NCBC mesh, after cooling i.e.
S/NCBC positive poles are obtained, prepared S/NCBC positive electrodes amount containing S is 82wt%.
A kind of Li-S batteries using the above-mentioned cell positive material assembling based on N doping carbonization bacteria celluloses：
Step 1, with the NaOH boilings of 1M after thickness is taken out for the BC diaphragms of 0.5mm from culture medium, then uses deionization
Water is rinsed up to cleaning solution in neutrality repeatedly, and freeze-drying afterwards obtains pure BC aeroges, after processing the pressing of BC aeroges
Under an inert atmosphere in 1000 DEG C of carbonization treatments 1h, ultralight CBC films are obtained.
Step 2, will be scattered in porous carbon CMK-3 in 1-METHYLPYRROLIDONE and is uniformly compound to lightweight by the method for film
CBC films surface.CMK-3 compound quantities are 0.12mg/cm2.The composite is used as into Li-S battery functi on interlayers.
Step 3, is 1.5mg cm by area density-2Pure BC aeroges be dipped in Nafion solution, Nafion is in BC
Middle compound quantity is 0.5mg cm-2, being fully transferred in 1M LiOH solution after immersion carries out lithiumation process, 80 DEG C of temperature holding, when
Between maintain 14h, freeze-drying afterwards, with the pressure of 0.2Mpa do pressing process, make as Li-S battery Nafion/BC barrier films
With.
Step 4, by the use of S/NCBC composites, to do positive pole, lithium metal be negative pole, Nafion/BC used as battery diaphragm, CBC
Function interlayer is placed in assembled battery between positive pole and barrier film.Electrolyte containing 1M LiTFSI in used in battery electrolyte,
The LiNO of 1.0wt% concentration3Additive, it is 1 that solvent is volume ratio:The mixed solution of 1 DME and DOL.
Embodiment 4
A kind of preparation method of the anode based on N doping carbonization bacteria celluloses, comprises the following steps that：
Step 1, deionized water flushing membrane excess surface is sent out after thickness is taken out for the BC diaphragms of 3.0mm from culture medium
Zymotic fluid, then freeze-drying obtains the BC aeroges of source containing N.
Step 2, will contain N sources BC aeroges do pressing process (0.2Mpa normal pressures), then under inert atmosphere protection in
1000 DEG C of insulation 3h, obtain NCBC aeroges.
Step 3, by NCBC aeroges infiltration to S/CS2In solution, 12h is stored at room temperature, is put into after taking-up in closed container,
24h is kept at a temperature of 300 DEG C, simple substance S is made in molten condition, and is equably diffused to inside NCBC mesh, after cooling i.e.
S/NCBC positive poles are obtained, prepared S/NCBC positive electrodes amount containing S is 90wt%.
A kind of Li-S batteries using the above-mentioned cell positive material assembling based on N doping carbonization bacteria celluloses：
Step 1, uses the NaOH boilings deionized water again of 1M after thickness is taken out for the BC diaphragms of 1.5mm from culture medium
Rinse up to cleaning solution in neutrality repeatedly, freeze-drying afterwards is obtained after pure BC aeroges are processed the pressing of BC aeroges lazy
In 1000 DEG C of carbonization treatments 1h under property atmosphere, ultralight CBC films are obtained.
Step 2, will be scattered in porous carbon CMK-3 in 1-METHYLPYRROLIDONE and is uniformly compound to lightweight by the method for film
CBC films surface.CMK-3 compound quantities are 0.20mg/cm2.The composite is used as into Li-S battery functi on interlayers.
Step 3, is 3.0mg cm by area density-2Pure BC aeroges be dipped in Nafion solution, Nafion is in BC
Middle compound quantity is 1.0mg cm-2, being fully transferred in 1M LiOH solution after immersion carries out lithiumation process, and temperature is kept for 100 DEG C,
Time maintains 14h, afterwards freeze-drying to do pressing with the pressure of 0.2Mpa and process, make as Li-S battery Nafion/BC barrier films
With.
Step 4, by the use of S/NCBC composites, to do positive pole, lithium metal be negative pole, Nafion/BC used as battery diaphragm, CBC
Function interlayer is placed in assembled battery between positive pole and barrier film.Electrolyte containing 1MLiTFSI, 1.0wt% in used in battery electrolyte
The LiNO of concentration3Additive, it is 1 that solvent is volume ratio:The mixed solution of 1 DME and DOL.
Comparative example 1
A kind of Li-S batteries, by method same as Example 3 S/NCBC positive poles, Nafion/BC battery diaphragms are prepared
And electrolyte, but the Li-S batteries in the comparative example without function interlayer between positive pole and barrier film.
Comparative example 2
A kind of Li-S batteries, by method same as Example 3 S/NCBC positive poles, function interlayer and electrolyte are prepared,
But the Li-S batteries in the comparative example substitute Nafion/BC battery diaphragms with business-like Celgard films.
Comparative example 3
A kind of Li-S batteries, by method same as Example 3 prepare function interlayer, Nafion/BC battery diaphragms and
Electrolyte, but the BC that the Li-S batteries in the comparative example are used to prepare positive pole is the pure BC aeroges without N sources.
Table 1 is each embodiment and comparative example battery in 800mA g-1Test result under current density
Knowable to the comparison of embodiment in table 1, the temperature of carbonisation affects battery performance.By embodiment 1 and enforcement
Example 2, the comparison of embodiment 3 understand that, when carburizing temperature is relatively low, battery specific capacity is relatively low, decay also very fast.By embodiment 3
Comparison with comparative example finds that positive pole N doping, the use of function interlayer, Nafion/BC barrier films can all significantly improve following for battery
Ring ability and coulombic efficiency.Think that this is mainly realized for the multistage of polysulfide diffusion from three different aspects
Suppress.The N element of doping in positive electrode can significantly increase the interphase interaction of carbon fiber and S and polysulfide, therefore, can be to many sulfurations
Inhibition is played in thing diffusion；The porous carbon of CBC sandwiching surfaces coating can effectively adsorb many sulfurations diffused out from positive electrode surface
Thing；The polysulfide for diffusing to battery diaphragm on a small quantity will be controlled by Nafion/BC barrier layers, and its mechanism model is shown in Fig. 2 institutes
Show.Additionally, compare discovery with comparative example 1 by embodiment 3, and it is minimum without the battery specific capacity of CBC function interlayers, illustrate CBC
Function interlayer can effectively reduce battery impedance, and can increase wetting capacity of the electrolyte to positive electrode.
Claims (9)
1. it is a kind of based on N doping be carbonized bacteria cellulose anode preparation method, it is characterised in that concrete steps are such as
Under：
Step 1, after bacteria cellulose diaphragm is taken out from culture medium, the unnecessary zymotic fluid on membrane removal surface is removed in washing, and freezing is dry
It is dry to obtain the bacteria cellulose aeroge containing nitrogen source；
Step 2, the bacteria cellulose aeroge pressing that will contain nitrogen source is processed, then the carbon at 800-1000 DEG C under an inert atmosphere
Change, obtain N doping carbonization bacteria cellulose aeroge；
Step 3, by N doping carbonization bacteria cellulose aeroge S/CS is impregnated in2In solution, after taking-up, under closed environment
130-300 DEG C is heat-treated, and makes simple substance S in molten condition, and equably diffuses to N doping carbonization bacteria cellulose airsetting
Inside glue mesh, the anode based on N doping carbonization bacteria cellulose, i.e. S/NCBC positive poles, wherein S/ are obtained after cooling
The amount containing S of NCBC anode electrode pieces is 75-90wt%.
2. preparation method as claimed in claim 1, it is characterised in that in step 1, the thickness of described bacteria cellulose diaphragm
For 1.5-3.0mm.
3. preparation method as claimed in claim 1, it is characterised in that in step 2, the pressure that described pressing is processed is
0.2Mpa, described carbonization time is 1-3h.
4. preparation method as claimed in claim 1, it is characterised in that in step 3, described dip time is 2-12h, described
Heat treatment time be 6-24h.
5. the electricity of the bacteria cellulose that is carbonized based on N doping that the preparation method as described in Claims 1-4 is arbitrary is prepared
Pond positive pole.
6. what a kind of preparation method using as described in Claims 1-4 is arbitrary was prepared is fine based on N doping carbonization bacterium
The preparation method of the Li-S batteries of the cell positive material assembling of dimension element, it is characterised in that comprise the following steps that：
Step 1, after bacteria cellulose diaphragm is taken out from culture medium, with the NaOH boilings of 1M, during washing is until cleaning solution is in
Property, freeze-drying obtains pure bacteria cellulose aeroge, afterwards by bacteria cellulose aeroge pressing process, then in inertia
In 800-1000 DEG C of carbonization under atmosphere, ultralight carbonization bacteria cellulose film is obtained；
Step 2, porous carbon is dispersed in 1-METHYLPYRROLIDONE, is combined porous carbon dispersion liquid by the method for film
To ultralight carbonization bacteria cellulose film surface, the compound quantity of porous carbon is 0.10-0.20mg/cm2, as carbonization bacteria cellulose
Function interlayer；
Step 3, pure bacteria cellulose aeroge is dipped in Nafion solution, is fully transferred to 1M LiOH solution after immersion
In carry out lithiumation process, temperature is kept for 60-100 DEG C, and pressing after freeze-drying is processed, as Nafion/BC barrier films, in barrier film
Compound quantities of the Nafion in pure bacteria cellulose aeroge is 0.2-1.0mg cm-2；
Step 4, with the sulfonic acid imide li electrolyte of bis trifluoromethyl containing 1M, the lithium nitrate additive of 1.0wt% concentration, solvent is
Volume ratio is 1:1 glycol dimethyl ether and the mixed solution of DOX, as electrolyte, with S/NCBC composites
For positive pole, lithium metal is negative pole, and Nafion/BC barrier films are battery diaphragm, carbonization bacteria cellulose function interlayer be placed in positive pole and
Li-S batteries are assembled between barrier film.
7. preparation method as claimed in claim 6, it is characterised in that in step 1, the thickness of described bacteria cellulose diaphragm
For 0.5-1.5mm.
8. preparation method as claimed in claim 6, it is characterised in that in step 3, described pure bacteria cellulose aeroge
Area density is 0.5-3.0mg cm-2, the described lithiumation time is 14h, and the pressure that described pressing is processed is 0.2Mpa.
9. Li-S batteries obtained in the preparation method as described in claim 6 to 8 is arbitrary.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109244579A (en) * | 2018-09-18 | 2019-01-18 | 余姚市鑫和电池材料有限公司 | A kind of preparation method of high-specific surface area ternary precursor powder |
| CN109962222A (en) * | 2019-03-04 | 2019-07-02 | 杭州电子科技大学 | A method of lithium sulfur battery anode material is prepared using bacteria cellulose aquagel |
| CN110212180A (en) * | 2019-05-22 | 2019-09-06 | 杭州电子科技大学 | A kind of preparation method and lithium-sulfur cell of lithium sulfide self-supporting carbon ball/carbon nano-fiber composite material |
| CN110600739A (en) * | 2019-08-22 | 2019-12-20 | 浙江工业大学 | Preparation method of metal lithium negative electrode protection layer material |
| CN110996717A (en) * | 2017-08-07 | 2020-04-10 | 日本电信电话株式会社 | Sheet-like mask |
| CN111540899A (en) * | 2020-05-06 | 2020-08-14 | 南京林业大学 | Conductive ternary composite material and preparation method and application thereof |
| CN111785939A (en) * | 2020-05-27 | 2020-10-16 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Nitrogen-doped carbon aerogel-sulfur composite electrode and preparation method and application thereof |
| CN112142034A (en) * | 2020-09-27 | 2020-12-29 | 武汉理工大学 | Preparation method of sulfur/carbon aerogel composite material |
| CN112391700A (en) * | 2020-11-06 | 2021-02-23 | 河北工业大学 | MOF-modified cellulosic material interlayer for lithium sulfur battery and preparation method |
| CN112820548A (en) * | 2020-12-30 | 2021-05-18 | 上海应用技术大学 | High-performance cellulose solution gel nano carbon material and preparation and application thereof |
| CN115424867A (en) * | 2022-08-12 | 2022-12-02 | 湖北工业大学 | Flexible super capacitor and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104157815A (en) * | 2014-08-22 | 2014-11-19 | 海南光宇生物科技有限公司 | Bacterial cellulose porous thin film and preparation method thereof |
-
2016
- 2016-12-26 CN CN201611218937.1A patent/CN106601990B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104157815A (en) * | 2014-08-22 | 2014-11-19 | 海南光宇生物科技有限公司 | Bacterial cellulose porous thin film and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| I.BAUER,S,等: "Reduced polysulfide shuttle in lithium –sulfur batteries using Nafion-based separators", 《JOURNAL OF POWER SOURCES》 * |
| SHIQI LI,等: "Gel based sulfur cathodes with a high sulfur content and large mass loading for high-performance lithium-sulfur batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| YANG HUANG，等: "Flexible cathodes and multifunctional interlayers based on carbonized bacterial cellulose for high-performance lithium-sulfur bateries", 《JOURNAL OF MATERIALS CHEMISTY A》 * |
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| CN109244579B (en) * | 2018-09-18 | 2020-07-03 | 余姚市鑫和电池材料有限公司 | Preparation method of ternary precursor powder with high specific surface area |
| CN109244579A (en) * | 2018-09-18 | 2019-01-18 | 余姚市鑫和电池材料有限公司 | A kind of preparation method of high-specific surface area ternary precursor powder |
| CN109962222A (en) * | 2019-03-04 | 2019-07-02 | 杭州电子科技大学 | A method of lithium sulfur battery anode material is prepared using bacteria cellulose aquagel |
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| CN111540899A (en) * | 2020-05-06 | 2020-08-14 | 南京林业大学 | Conductive ternary composite material and preparation method and application thereof |
| CN111785939A (en) * | 2020-05-27 | 2020-10-16 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Nitrogen-doped carbon aerogel-sulfur composite electrode and preparation method and application thereof |
| CN112142034A (en) * | 2020-09-27 | 2020-12-29 | 武汉理工大学 | Preparation method of sulfur/carbon aerogel composite material |
| CN112391700A (en) * | 2020-11-06 | 2021-02-23 | 河北工业大学 | MOF-modified cellulosic material interlayer for lithium sulfur battery and preparation method |
| CN112391700B (en) * | 2020-11-06 | 2022-04-26 | 河北工业大学 | MOF-modified cellulosic material interlayer for lithium sulfur battery and preparation method |
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