CN108807808A - A kind of biomass carbon aeroge is modified lithium-sulfur cell dedicated diaphragm and preparation method thereof and lithium-sulfur cell - Google Patents
A kind of biomass carbon aeroge is modified lithium-sulfur cell dedicated diaphragm and preparation method thereof and lithium-sulfur cell Download PDFInfo
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- CN108807808A CN108807808A CN201810998056.9A CN201810998056A CN108807808A CN 108807808 A CN108807808 A CN 108807808A CN 201810998056 A CN201810998056 A CN 201810998056A CN 108807808 A CN108807808 A CN 108807808A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M50/431—Inorganic 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- 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
Abstract
The invention discloses a kind of biomass carbon aeroges to be modified lithium-sulfur cell dedicated diaphragm, including septum body and coated in septum body close to the modified coating of a positive side surface, modified coating includes shaddock ped based biomass charcoal-aero gel, conductive agent and binder, and modified coating has porous structure.The modified coating shaddock ped based biomass carbon aerogel material of the dedicated diaphragm and the Porous barriers of conductive agent can allow lithium ion to pass through, can also there are certain blocking and suction-operated to the polysulfide generated during positive redox reaction, it is more advantageous to battery performance and cycle performance.The invention also discloses the preparation methods that a kind of biomass carbon aeroge is modified lithium-sulfur cell dedicated diaphragm, method is relatively simple, novel diaphragm need not be developed, it is only necessary to which one layer of modified material of coating can be used on the existing normal diaphragm of commercialization, and time and expense is greatly saved.The invention also discloses the lithium-sulfur cells using dedicated diaphragm assembling.
Description
Technical field
The invention belongs to field of lithium ion battery more particularly to a kind of biomass carbon aeroge be modified lithium-sulfur cell it is special every
Film and preparation method thereof and lithium-sulfur cell.
Background technology
Lithium-sulfur cell is secondary cell of the metal lithium sheet as negative material using sulphur as positive electrode, theoretical specific volume
Amount and battery theory are respectively 1675mAh/g and 2600Whk/g than energy.And element sulphur content in the earth's crust is higher, and be ring
Border friendly element, of low cost, in electric vehicle, the fields such as consumer electronics have good application prospect.But lithium-sulfur cell
In application process there is also certain problem, most important problem, which is the intermediate discharging product of lithium-sulfur cell, to be dissolved in
In machine electrolyte, increase the viscosity of electrolyte, reduces the electrical conductance of ion.More sulphions can migrate between positive and negative anodes, occur
Shuttle effect, so as to cause the loss of active material and the waste of electric energy, the polysulfide of dissolving can be diffused into negative across diaphragm
Pole destroys the solid electrolyte interface SEI films of cathode with negative reaction.
So the shuttle effect of blocking or inhibition polysulfide is maximally efficient as lithium-sulfur cell performance is improved always
One of method.It is exactly in lithium sulphur if 105280867 A of Chinese patent CN disclose a kind of method of modifying of lithium-sulfur cell diaphragm
One layer is coated on battery normal commercial diaphragm is added with Ketjen black coated metal oxide modified coating.Nanometer base Ketjen black and gold
Belonging to the compound Porous barriers of oxide can allow lithium ion to pass through, furthermore it is also possible to during to positive redox reaction
The polysulfide of generation has certain blocking and suction-operated, to greatly improve the capacity of lithium-sulfur cell and prolonged
Cycle performance.But the barrier layer one-tenth porosity that these materials are formed is limited, greatly limits the absorption to polysulfide, and material
Cost itself is higher, so, it is very necessary as the barrier layer of diaphragm to research and develop a kind of strong and cheap material of adsorption capacity.
Invention content
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
The strong and cheap biomass carbon aeroge of kind adsorption capacity is modified lithium-sulfur cell dedicated diaphragm and preparation method thereof and uses this specially
The lithium-sulfur cell formed with diaphragm.
In order to solve the above technical problems, technical solution proposed by the present invention is：
A kind of biomass carbon aeroge is modified lithium-sulfur cell dedicated diaphragm, including septum body and is coated in the diaphragm sheet
The modified coating of the close positive side surface of body, the modified coating include shaddock ped based biomass charcoal-aero gel, conductive agent and glue
Agent is tied, the modified coating has porous structure.
In lithium-sulfur cell, the loss of polysulfide produces " shuttle effect ", so as to cause active material loss and
The waste of electric energy, so carrying out blocking to polysulfide becomes the key of promotion lithium-sulfur cell performance.Due to biomass carbon base
The presence of material porous structure, the Porous barriers that shaddock ped based biomass carbon aerogel material and conductive agent are formed can allow lithium from
Son passes through；Meanwhile biomass carbon sill has larger specific surface area, excellent electric conductivity, absorption property and preparation
The features such as method is simple, more vulcanizations of the modified coating being made from it for generation during redox reaction in lithium-sulfur cell
Object has certain blocking and suction-operated, blocks the shuttle of polysulfide, effectively inhibits " shuttle effect ", to significantly
Improve the capacity of lithium-sulfur cell and prolonged cycle performance.
It is in black that biomass carbon aeroge, which is a kind of mainly appearance made of carbonaceous material, internal pore structure is flourishing,
Large specific surface area is provided with superior adsorption capacity, therefore greatly enhances the adsorption energy of modified diaphragm Porous barriers
Power improves the capacity and cycle life of lithium-sulfur cell.The raw material that shaddock ped based biomass carbon aerogel material uses in the present invention
Shaddock ped, compared to other biological matter Carbon Materials, containing abundant plant fiber and a large amount of functional group in shaddock ped, such as hydroxyl, carboxylic
Base and amino etc. are a kind of sorbing materials with fine development prospect.Shaddock ped is made after charcoal still with very strong
Adsorption capacity can effectively adsorb polysulfide in lithium-sulfur cell.In addition, shaddock ped is renewable resource, price ten
Divide cheaply, and derive from a wealth of sources, is easy to obtain, preparation process is also relatively easy, is suitble to commercially produce, by biomass carbon aeroge
In material application to battery, the sustainable use of resource, green pollution-free are realized.
Shaddock ped based biomass carbon aerogel material and conductive agent are used in modified coating, do not use expensive metal oxygen
Compound material, not only improves the chemical property of the lithium-sulfur cell using the modified diaphragm, but also reduces to a certain extent
The production cost of battery is suitable for commercially producing.
Above-mentioned biomass carbon aeroge is modified lithium-sulfur cell dedicated diaphragm, it is preferred that the septum body be it is commercial every
The thickness of film Celgard2400, the modified coating are 10~200 μm.
Preferably, the conductive agent is one or more of Ketjen black, acetylene black and Super-P, these types of conductive agent
The electric conductivity of modified coating can be improved to a certain extent；The binder is Kynoar, polyvinyl alcohol and poly- four
Modified coating material can be fixed on septum body by the selection of one or more of vinyl fluoride, these types of binder well
On, ensure not falling off in battery recycles for a long time；The matter of the shaddock ped based biomass charcoal-aero gel, conductive agent and binder
Amount is than being (5~8):(1~3):(2~5).
Preferably, the shaddock ped based biomass charcoal-aero gel is freeze-dried by shaddock ped after hydro-thermal reaction, then in nitrogen
Pyrolysis obtains in atmosphere.
Preferably, doped with nitrogen and boron element in the shaddock ped based biomass charcoal-aero gel.Pass through different elements
The electronic structure that can change inside Carbon Materials is introduced, so as to improve the electric conductivity of material.Other than physical barriers and absorption, change
It is considered as a kind of means of effective fixed polysulfide to learn absorption, certain by will be formed between nitrogen and boron element and carbon
Chemical bond and be introduced on the skeleton of shaddock ped based biomass charcoal-aero gel Carbon Materials, this method can change charcoal material surface
With internal electronic structure, so as to improve the electric conductivity of material.Therefore, nitrogen and boron element doping Carbon Materials to a certain extent may be used
To generate strong chemisorption to polysulfide by the effect between charge, to the more sulphur of highly effective fixation
Compound promotes the performance of lithium-sulfur cell.
Based on a total technical concept, the present invention also provides a kind of biomass carbon aeroge be modified lithium-sulfur cell it is special every
The preparation method of film, includes the following steps：
(1) shaddock ped is subjected to hydro-thermal reaction, then is freeze-dried, is then pyrolyzed in nitrogen atmosphere, obtain shaddock
Scytoblastema biomass carbon aerogel material；
(2) binder is mixed with solvent, obtained binder solution and the shaddock obtained after conductive agent, the step (1)
Scytoblastema biomass carbon aerogel material mixes, and coating paste is obtained after mechanical agitation is uniform；
(3) coating paste obtained after the step (2) is uniformly coated on septum body close to just on coating machine
Pole side, it is dry to be modified lithium-sulfur cell dedicated diaphragm to get to the biomass carbon aeroge.
Above-mentioned preparation method, it is preferred that in the step (1), hydro-thermal reaction specifically comprises the following steps：Shaddock ped is gone
Hard epidermis, stripping and slicing are cleaned and are put into hydrothermal reaction kettle, 130~200 DEG C of 8~12h of hydro-thermal reaction in air dry oven, so
Impregnated 1~3 day in 50~80 DEG C of hot baths afterwards, remove soluble impurity, then be placed in -30~10 DEG C of environment freezing 12~
After 36h, then it is placed in 12~48h of freeze-drying in vacuum freezing drying oven；Pyrolysis temperature is 600 DEG C~1000 DEG C.600 DEG C~
Shaddock ped is pyrolyzed within the temperature range of 1000 DEG C can obtain the carbonization structure with void defects, and this is for the electric conductivity of material
It is most important；In addition, the groups such as hydroxyl, carboxyl are pyrolyzed disappearance at such a temperature, material forms maximized porous structure.
Preferably, in the step (2), solvent is one or more of ethyl alcohol, acetone and N-Methyl pyrrolidone；It is viscous
The mass ratio for tying agent and solvent is (1~3):(10~30)；Churned mechanically speed is 500~1000r/min, and mixing time is
2~5min.
Preferably, in the step (3), drying temperature is 20~40 DEG C, and drying time is 12~48h.
Based on a total technical concept, the present invention also provides a kind of lithium-sulfur cell, including anode, cathode, electrolyte and
Diaphragm, the diaphragm are that above-mentioned biomass carbon aeroge is modified lithium-sulfur cell dedicated diaphragm, and described just extremely carbon sulphur is compound just
Pole, the cathode are metal lithium sheet, and the electrolyte includes the mixture of 1,3-dioxolane and glycol dimethyl ether, double trifluoros
Pyrovinic acid Asia amide lithium and lithium nitrate.Wherein, in the mixture of 1,3-dioxolane and glycol dimethyl ether, 1,3- dioxy penta
The volume ratio of ring and glycol dimethyl ether is 1:1, a concentration of 1~3M of bis trifluoromethyl sulfonic acid Asia amide lithium, nitre in electrolyte
Sour lithium concentration is 0.1~0.3M.
The present invention is mainly according to following invention thinking：Select lithium-sulfur cell be commonly commercialized normal diaphragm as this
Modified object, to be commercialized normal diaphragm as matrix, in the film, one layer of coating contains shaddock ped on the surface of positive side
The Porous barriers of based biomass carbon aerogel material and conductive agent (preferably use the shaddock ped based biomass charcoal gas of dual element doping
Gel), and use the modified diaphragm as the dedicated diaphragm of lithium-sulfur cell, lithium is assembled using carbon sulphur composite material as positive electrode
Sulphur battery.
Compared with prior art, beneficial effects of the present invention are：
1, biomass carbon aeroge of the invention is modified lithium-sulfur cell dedicated diaphragm, shaddock ped based biomass carbon aerogel material
Lithium ion can be allowed to pass through with the Porous barriers of conductive agent, furthermore it is also possible to being generated during positive redox reaction
Polysulfide have certain a blocking and suction-operated, wherein shaddock ped based biomass carbon aerogel material has higher specific surface
Product, therefore its superior adsorption capacity is imparted, so the addition of shaddock ped based biomass carbon aerogel material is more conducive to
Absorption to polysulfide, the more effective fruit of shuttle than the Porous barriers blocking polysulfide of metal oxide formation, to electricity
Pond chemical property and cycle performance are more advantageous.
2, biomass carbon aeroge of the invention is modified lithium-sulfur cell dedicated diaphragm, and raw material of wood-charcoal is adulterated using nitrogen and boron element
Material can generate strong chemisorption by the effect between charge to polysulfide to a certain extent, to
Highly effective fixed polysulfide, promotes the performance of lithium-sulfur cell.
3, biomass carbon aeroge of the invention is modified lithium-sulfur cell dedicated diaphragm, compared to other porous carbon based materials,
Containing abundant plant fiber and a large amount of functional group, such as hydroxyl, carboxyl and amino in its raw material shaddock ped, being one kind has very
The sorbing material of good development prospect, shaddock ped, which is made after charcoal, still has very strong adsorption capacity, can be to lithium-sulfur cell
Middle polysulfide is effectively adsorbed；In addition, shaddock ped is renewable resource, price is very cheap, and derives from a wealth of sources, and is easy to obtain
It takes, preparation process is also relatively easy, is suitble to commercially produce, and biomass carbon aerogel material is applied in battery, is realized
The sustainable use of resource, green pollution-free.
4, preparation method of the invention, the shaddock ped based biomass carbon aerogel material being prepared belong to biomass carbon material
One kind, the electric conductivity of biomass carbon aerogel material is mainly since in carbonization process, biomass carbon aeroge occurs
It is graphitized crystal, with the raising of carbonization temperature, graphite crystal gradually gathers to neat, therefore electric conductivity also gradually increases, should
Also there is shaddock ped based biomass carbon aerogel material certain excellent electric conductivity, modified lithium-sulfur cell dedicated diaphragm to have
High conductivity and good chemical stability；The preparation method of the present invention is relatively simple, need not develop novel diaphragm, only
It needs one layer of modified material of coating on the existing normal diaphragm of commercialization to can be used, time and expense is greatly saved.
5, the present invention is modified lithium-sulfur cell dedicated diaphragm assembled battery using biomass carbon aeroge, inhibits lithium well
The shuttle effect of polysulfide in sulphur battery, battery have good charge-discharge performance and high rate performance.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the scanning electricity that the dual element prepared in the embodiment of the present invention 1 adulterates shaddock ped based biomass carbon aerogel material
Mirror (a) and transmission electron microscope (b, c) figure.
Fig. 2 be the embodiment of the present invention 1 prepared by dual element adulterate biomass carbon aeroge be modified lithium-sulfur cell it is special every
The volt-ampere curve figure of the lithium-sulfur cell of film assembling.
Fig. 3 is that the biomass carbon aeroge prepared by the embodiment of the present invention 1,2 is modified the assembling of lithium-sulfur cell dedicated diaphragm
The cycle performance curve graph of lithium-sulfur cell 500 circle of cycle in the case where charge-discharge magnification is 1C.
Fig. 4 is that the biomass carbon aeroge prepared by the embodiment of the present invention 2,3,4 is modified the assembling of lithium-sulfur cell dedicated diaphragm
Lithium-sulfur cell and comparative example prepared by lithium-sulfur cell 200 circle of cycle in the case where charge-discharge magnification is 1C cycle performance it is bent
Line chart.
Specific implementation mode
To facilitate the understanding of the present invention, the present invention is done below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but protection scope of the present invention is not limited to following specific examples.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of dual element doping biomass carbon aeroge modification lithium-sulfur cell dedicated diaphragm of the present invention, including commercial diaphragm
Celgard2400 ontologies and coated in the septum body close to the modified coating of a positive side surface, modified coating has more
Pore structure, dual element doping shaddock ped based biomass charcoal-aero gel, conductive agent Super-P and binder polyvinylidene fluoride in modified coating
The mass ratio of alkene (PVDF) is about 6:1:3, the dual element of doping is nitrogen and boron element, and the thickness of modified coating is 15 μm of left sides
It is right.
This implementation dual element adulterates the preparation method that shaddock ped based biomass charcoal-aero gel is modified lithium-sulfur cell dedicated diaphragm, packet
Include following steps：
(1) preparation of dual element doping shaddock ped based biomass carbon aerogel material：Shaddock ped goes hard epidermis, stripping and slicing, washing
Totally, it is put into hydrothermal reaction kettle, 180 DEG C of hydro-thermal reaction 10h in air dry oven impregnate 2 days in 70 DEG C of hot baths, removal
Soluble impurity after -20 DEG C of freezings for 24 hours, then is placed in vacuum freezing drying oven and is freeze-dried 48h；The bulk material that will be obtained
It enters magnetic agitation in ammoniumborate solution and again passes by freeze-drying 48h for 24 hours, after taking-up；Finally, by material in nitrogen atmosphere
800 DEG C of pyrolysis 1h in enclosing, grinding, i.e., powdered dual element doping shaddock ped based biomass carbon aerogel material (such as Fig. 1)；
(2) preparation of binder solution：This time dual element doping shaddock ped based biomass charcoal-aero gel coating commercialization is normal
Binder used by diaphragm is PVDF, and solvent is N-Methyl pyrrolidone (NMP), and the two is with 1:25 mass ratio mixing,
The binder solution that magnetic agitation 4h or so is mixed；
(3) dual element doping shaddock ped based biomass charcoal-aero gel coating is commercialized normal diaphragm：Take the double base that 0.09g is above-mentioned
Element doping shaddock ped based biomass carbon aerogel material, (PVDF and NMP's is mixed for 0.015g Super-P, 1.125g binder solution
Close solution) it is uniformly mixed in beaker, it is put into mechanical agitation 3min in blender and obtains coating paste；
(4) on automatic coating machine with scraper by the coating paste of above-mentioned preparation be uniformly coated on Celgard2400 every
Film is on the surface of positive side, for 24 hours by the 25 DEG C of dryings of coated modified diaphragm room temperature, you can obtains dual element doping life
Substance charcoal-aero gel is modified lithium-sulfur cell dedicated diaphragm.
Mapping scanning results are shown in Fig. 1 shown in (a), shown in (b) in TEM results such as Fig. 1, (c).As shown in Figure 1, double
More regular strip network structure is presented in element doping shaddock ped based biomass carbon surface, and is dispersed with non-uniform hole, nitrogen member
Element and boron element are also more evenly distributed on Carbon Materials, illustrate that doping achieves certain effect.These results indicate that double
Element doping shaddock ped based biomass charcoal produces pore space structure not of uniform size, and these holes are in cell oxidation reduction process
The polysulfide of generation plays certain suction-operated.
Embodiment 2：
A kind of pure shaddock ped based biomass charcoal-aero gel modification lithium-sulfur cell dedicated diaphragm of the present invention, including commercial diaphragm
Celgard2400 ontologies and coated in the septum body close to the modified coating of a positive side surface, modified coating has more
Pore structure, shaddock ped based biomass charcoal-aero gel in modified coating, conductive agent Super-P and binder Kynoar (PVDF)
Mass ratio is about 6:1:3, the thickness of modified coating is 15 μm or so.
This implements the preparation method that pure shaddock ped based biomass charcoal-aero gel is modified lithium-sulfur cell dedicated diaphragm, including following step
Suddenly：
(1) preparation of pure shaddock ped based biomass carbon aerogel material：Shaddock ped goes hard epidermis, stripping and slicing, washes clean to be put into
In hydrothermal reaction kettle, 180 DEG C of hydro-thermal reaction 10h in air dry oven impregnate 2 days in 70 DEG C of hot baths, and removal is soluble miscellaneous
Matter after -20 DEG C of freezings for 24 hours, then is placed in vacuum freezing drying oven and is freeze-dried 48h；Finally, by material in nitrogen atmosphere
800 DEG C of pyrolysis 1h, grinding, i.e. powdered pure shaddock ped based biomass carbon aerogel material；
(2) preparation of binder solution：This time pure shaddock ped based biomass charcoal-aero gel coating is commercialized normal diaphragm and is adopted
Binder is PVDF, and solvent NMP, the two is with mass ratio for 1:25 ratio mixing, magnetic agitation 4h or so are mixed
The binder solution of conjunction；
(3) pure shaddock ped based biomass charcoal-aero gel coating is commercialized normal diaphragm：Take the pure shaddock ped base biology that 0.09g is above-mentioned
Matter carbon aerogel material, 0.015g Super-P, 1.125g binder solution (mixed solution of PVDF and NMP) mix in beaker
It closes uniformly, is put into mechanical agitation 3min in blender and obtains coating paste；
(4) on automatic coating machine with scraper by the coating paste of above-mentioned preparation be uniformly coated on Celgard2400 every
Film is on the surface of positive side, for 24 hours by the 25 DEG C of dryings of coated modified diaphragm room temperature, you can obtains pure shaddock ped base biology
Matter charcoal-aero gel is modified lithium-sulfur cell dedicated diaphragm.
The pure shaddock ped based biomass charcoal-aero gel of the present embodiment is measured using BET method and 1 dual element of embodiment adulterates shaddock ped base
The specific surface area of biomass carbon aerogel material, the data of total pore volume and average pore size, as shown in table 1.
Table 1：The data of pure shaddock ped based biomass charcoal-aero gel and dual element doping shaddock ped based biomass carbon aerogel material
Comparison
As shown in Table 1, the specific surface area of dual element doping shaddock ped carbon aerogel material is by undoped 495.66m2g-1Increase
It is added to 674.53m2g-1, due to the promotion of material specific surface area after doping, so diagram modification coating is for redox reaction
Enhancing is played the role of in the absorption of the polysulfide of middle generation, while also playing certain booster action for the conduction of lithium ion.
Embodiment 3：
A kind of pure shaddock ped based biomass charcoal-aero gel modification lithium-sulfur cell dedicated diaphragm of the present invention, including commercial diaphragm
Celgard2400 ontologies and coated in the septum body close to the modified coating of a positive side surface, modified coating has more
Pore structure, shaddock ped based biomass charcoal-aero gel in modified coating, conductive agent Super-P and binder Kynoar (PVDF)
Mass ratio is about 7:1:2, the thickness of modified coating is 15 μm or so.
This implements the preparation method that pure shaddock ped based biomass charcoal-aero gel is modified lithium-sulfur cell dedicated diaphragm, including following step
Suddenly：
(1) preparation of pure shaddock ped based biomass carbon aerogel material：Shaddock ped goes hard epidermis, stripping and slicing, washes clean to be put into
In hydrothermal reaction kettle, 180 DEG C of hydro-thermal reaction 10h in air dry oven impregnate 2 days in 70 DEG C of hot baths, and removal is soluble miscellaneous
Matter after -20 DEG C of freezings for 24 hours, then is placed in vacuum freezing drying oven and is freeze-dried 48h；Finally, by material in nitrogen atmosphere
700 DEG C of pyrolysis 1h, grinding, i.e. powdered pure shaddock ped based biomass carbon aerogel material；
(2) preparation of binder solution：This time pure shaddock ped based biomass charcoal-aero gel coating is commercialized normal diaphragm and is adopted
Binder is PVDF, and solvent NMP, the two is with mass ratio for 1:25 ratio mixing, magnetic agitation 4h or so are mixed
The binder solution of conjunction；
(3) pure shaddock ped based biomass charcoal-aero gel coating is commercialized normal diaphragm：Take the pure shaddock ped base biology that 0.07g is above-mentioned
Matter carbon aerogel material, 0.01g Super-P, 0.52g binder solution (mixed solution of PVDF and NMP) mix in beaker
Uniformly, it is put into mechanical agitation 3min in blender and obtains coating paste；
(4) on automatic coating machine with scraper by the coating paste of above-mentioned preparation be uniformly coated on Celgard2400 every
Film is on the surface of positive side, for 24 hours by the 25 DEG C of dryings of coated modified diaphragm room temperature, you can obtains pure shaddock ped base biology
Matter charcoal-aero gel is modified lithium-sulfur cell dedicated diaphragm.
Embodiment 4：
A kind of pure shaddock ped based biomass charcoal-aero gel modification lithium-sulfur cell dedicated diaphragm of the present invention, including commercial diaphragm
Celgard2400 ontologies and coated in the septum body close to the modified coating of a positive side surface, modified coating has more
Pore structure, shaddock ped based biomass charcoal-aero gel in modified coating, conductive agent Super-P and binder Kynoar (PVDF)
Mass ratio is about 5:2:3, the thickness of modified coating is 15 μm or so.
This implements the preparation method that pure shaddock ped based biomass charcoal-aero gel is modified lithium-sulfur cell dedicated diaphragm, including following step
Suddenly：
(1) preparation of pure shaddock ped based biomass carbon aerogel material：Shaddock ped goes hard epidermis, stripping and slicing, washes clean to be put into
In hydrothermal reaction kettle, 180 DEG C of hydro-thermal reaction 10h in air dry oven impregnate 2 days in 70 DEG C of hot baths, and removal is soluble miscellaneous
Matter after -20 DEG C of freezings for 24 hours, then is placed in vacuum freezing drying oven and is freeze-dried 48h；Finally, by material in nitrogen atmosphere
600 DEG C of pyrolysis 1h, grinding, i.e. powdered pure shaddock ped based biomass carbon aerogel material；
(2) preparation of binder solution：This time pure shaddock ped based biomass charcoal-aero gel coating is commercialized normal diaphragm and is adopted
Binder is PVDF, and solvent NMP, the two is with mass ratio for 1:25 ratio mixing, magnetic agitation 4h or so are mixed
The binder solution of conjunction；
(3) pure shaddock ped based biomass charcoal-aero gel coating is commercialized normal diaphragm：Take the pure shaddock ped base life that 0.075g is above-mentioned
Substance carbon aerogel material, 0.03g Super-P, 1.125g binder solution (mixed solution of PVDF and NMP) are in beaker
It is uniformly mixed, is put into mechanical agitation 3min in blender and obtains coating paste；
(4) on automatic coating machine with scraper by the coating paste of above-mentioned preparation be uniformly coated on Celgard2400 every
Film is on the surface of positive side, for 24 hours by the 25 DEG C of dryings of coated modified diaphragm room temperature, you can obtains pure shaddock ped base biology
Matter charcoal-aero gel is modified lithium-sulfur cell dedicated diaphragm.
Embodiment 5：
A kind of lithium-sulfur cell of the present invention, including anode, cathode, electrolyte and diaphragm, diaphragm are prepared for Examples 1 to 4
Obtained biomass carbon aeroge is modified lithium-sulfur cell dedicated diaphragm, and just extremely carbon sulphur anode composite, cathode are metal lithium sheet, institute
It is the mixture including bis trifluoromethyl sulfonic acid Asia amide lithium, 1,3- dioxolanes and glycol dimethyl ether to state electrolyte.
The preparation method of the lithium-sulfur cell, includes the following steps：
(1) prepared by positive electrode：It takes 1g Ketjen black powder, 4g sulphur, 10g absolute ethyl alcohols to be placed in ball grinder, uses ball mill
The positive and negative rotation alternate rotation 4h under the rotating speed of 800r/min takes out spheroidal graphite tank and is placed in 45 DEG C of air dry ovens dry 12h, then
The mixture of Ketjen black and sulphur is placed in the reaction kettle liner of polytetrafluoroethylene (PTFE) and is placed in 155 DEG C of heat treatment 10h in batch-type furnace,
Obtain Ketjen black-sulphur composite material；
(2) prepared by lithium-sulphur cell positive electrode：0.1g PVDF are taken to be uniformly mixed with 4.9gN- methyl pyrrolidones (NMP), then magnetic
Power stirring 4h obtains binder, takes the carbon sulphur composite positive pole of the above-mentioned preparations of 0.14g, 0.02g Super-P, what 0.5g was prepared
Binder is uniformly mixed, and mechanical agitation 4min obtains mixed slurry under the rotating speed of 800r/min, then with scraper in automatic coating
Above-mentioned mixed slurry is uniformly coated on utter misery aluminium foil on machine, the positive pole aluminium foil coated is put into air dry oven 50 DEG C
Drying is for 24 hours, you can obtains carbon sulphur anode composite；
(3) lithium-sulfur cell is assembled：The carbon sulphur anode composite that will be obtained in step (2), life prepared by above example 1~4
Substance charcoal is modified lithium-sulfur cell dedicated diaphragm, cathode of lithium, and organic electrolyte assembles knob in glove box of the water oxygen value less than 1ppm
Detain lithium-sulfur cell；Wherein organic electrolyte includes：1M LiTFSI (bis trifluoromethyl sulfonic acid Asia amide lithium)+0.1M LiNO3(nitre
Sour lithium)+DOL (1,3-dioxolane)/DME (glycol dimethyl ether), the volume ratio of 1,3-dioxolane and glycol dimethyl ether
It is 1:1.
The dual element doping biomass carbon aeroge prepared using embodiment 1 is modified the lithium of lithium-sulfur cell dedicated diaphragm assembling
Sulphur battery, volt-ampere curve figure are as shown in Figure 2.As shown in Figure 2, the electricity for the diaphragm that dual element doping shaddock ped carbon aerogel material is modified
The reduction peak in pond is 2.02V, and higher recovery voltage shows that the Chemical Kinetics of inside battery obtains certain improvement, this
Also imply that dual element doping shaddock ped carbon aerogel material coating has catalytic action to sulphur reduction.At the same time we can be with
Observe that the battery for the diaphragm being modified with dual element doping shaddock ped carbon aerogel material shows sharp and higher oxidation
With reduction peak, this shows that dual element doping shaddock ped carbon aerogel material coating has good electric conductivity, improves inside battery
Kinetics.
The lithium sulphur of lithium-sulfur cell dedicated diaphragm assembling is modified using biomass carbon aeroge prepared by above example 1~4
Battery carries out cycle performance test under the conditions of 1C.The lithium-sulfur cell loop test result of the diaphragm assembling of embodiment 1,2 is as schemed
Shown in 3, the results are shown in Figure 4 for the lithium-sulfur cell loop test of the diaphragm assembling of embodiment 2,3,4.
From the figure 3, it may be seen that the lithium-sulfur cell 0.1C of 1 dual element of embodiment doping shaddock ped carbon aerogel material modified diaphragm assembling
First discharge specific capacity is 1463.6mAh/g, and specific discharge capacity is 586.6mAh/g after 1C cycles 500 are enclosed, and coulombic efficiency is higher than
98.9%, relative to the battery of 2 pure shaddock ped based biomass charcoal material modification diaphragm of embodiment assembling, can be evident that double
The cycle performance and high rate performance of the lithium-sulfur cell of element doping shaddock ped carbon aerogel material modified diaphragm assembling are obtained for
Prodigious promotion.
As shown in Figure 4, pure shaddock ped charcoal-aero gel modified diaphragm battery 0.1C first discharge specific capacities are 1152.6mAh/g,
For specific discharge capacity still up to 567.5mAh/g, coulombic efficiency is higher than 99% after 200 circle of 1C cycles.
Comparative example：
A kind of lithium-sulfur cell, the diaphragm used are common commercial diaphragm Celgard2400.
The preparation method of the lithium-sulfur cell of this comparative example, includes the following steps：
(1) prepared by positive electrode：It takes 1g Ketjen black powder, 4g sulphur, 10g absolute ethyl alcohols to be placed in ball grinder, uses ball mill
The positive and negative rotation alternate rotation 4h under the rotating speed of 800r/min takes out spheroidal graphite tank and is placed in 45 DEG C of air dry ovens dry 12h, then
The mixture of Ketjen black and sulphur is placed in the reaction kettle liner of polytetrafluoroethylene (PTFE) and is placed in 155 DEG C of heat treatment 10h in batch-type furnace,
Obtain Ketjen black~sulphur composite material；
(2) prepared by lithium-sulphur cell positive electrode：0.1g PVDF are taken to be uniformly mixed with 4.9g N-Methyl pyrrolidones (NMP), then
Magnetic agitation 4h obtains binder, takes the carbon sulphur composite positive pole of the above-mentioned preparations of 0.14g, 0.02g Super-P, and 0.5g is prepared
Binder be uniformly mixed, mechanical agitation 4min obtains mixed slurry under the rotating speed of 800r/min, then is being applied automatically with scraper
Above-mentioned mixed slurry is uniformly coated on utter misery aluminium foil on cloth machine, the positive pole aluminium foil coated is put into 50 in air dry oven
It is DEG C dry for 24 hours, you can carbon sulphur anode composite.
(3) lithium-sulfur cell is assembled：The carbon sulphur anode composite that will be obtained in step (2), common commercial diaphragm
Celgard2400, cathode of lithium, organic electrolyte 1M LiTFSI (bis trifluoromethyl sulfonic acid Asia amide lithium)+0.1M LiNO3(nitre
Sour lithium)+DOL (1,3-dioxolane)/DME (glycol dimethyl ether), assemble button in glove box of the water oxygen value less than 1ppm
Lithium-sulfur cell.
The lithium-sulfur cell prepared to this comparative example carries out cycle performance test at 1C, institute in loop test result such as Fig. 4
Show.As shown in Figure 4, the battery of pure shaddock ped charcoal biomass carbon material modification diaphragm assembling is added in comparison, uses commercialization diaphragm electricity
The cycle performance in pond is worse, and 351.3mAh/g is had fallen to after 200 circles, and uses the pure shaddock ped charcoal biomass raw material of wood-charcoal of the present invention
Expect the battery of modified diaphragm assembling, chemical property and cycle performance are more advantageous.
It is analyzed in conjunction with Fig. 3 and Fig. 4, relative to the battery of pure shaddock ped based biomass charcoal material modification diaphragm assembling, dual element
The cycle performance and high rate performance of the lithium-sulfur cell of doping shaddock ped carbon aerogel material modified diaphragm assembling are obtained for very big
Promotion；Relative to the battery of common commercial diaphragm assembling, the shaddock ped based biomass charcoal for being coated with the present invention is modified lithium sulphur electricity
The cycle performance and high rate performance of the battery of pond dedicated diaphragm assembling are obtained for prodigious promotion.
Claims (10)
1. a kind of biomass carbon aeroge is modified lithium-sulfur cell dedicated diaphragm, which is characterized in that including septum body and be coated in
The septum body close to a positive side surface modified coating, the modified coating include shaddock ped based biomass charcoal-aero gel,
Conductive agent and binder, the modified coating have porous structure.
2. biomass carbon aeroge according to claim 1 is modified lithium-sulfur cell dedicated diaphragm, which is characterized in that it is described every
Membrane body is commercial diaphragm Celgard2400, and the thickness of the modified coating is 10~200 μm.
3. biomass carbon aeroge according to claim 1 is modified lithium-sulfur cell dedicated diaphragm, which is characterized in that described to lead
Electric agent is one or more of Ketjen black, acetylene black and Super-P；The binder be Kynoar, polyvinyl alcohol and
One or more of polytetrafluoroethylene (PTFE)；The mass ratio of the shaddock ped based biomass charcoal-aero gel, conductive agent and binder is (5
~8):(1~3):(2~5).
4. biomass carbon aeroge according to claim 1 is modified lithium-sulfur cell dedicated diaphragm, which is characterized in that the shaddock
Scytoblastema biomass carbon aeroge is freeze-dried by shaddock ped after hydro-thermal reaction, then is pyrolyzed and is obtained in nitrogen atmosphere.
5. biomass carbon aeroge according to any one of claims 1 to 4 is modified lithium-sulfur cell dedicated diaphragm, feature
It is, doped with nitrogen and boron element in the shaddock ped based biomass charcoal-aero gel.
6. a kind of biomass carbon aeroge as described in any one of Claims 1 to 5 is modified the preparation of lithium-sulfur cell dedicated diaphragm
Method includes the following steps：
(1) shaddock ped is subjected to hydro-thermal reaction, then is freeze-dried, is then pyrolyzed in nitrogen atmosphere, obtain shaddock ped base
Biomass carbon aerogel material；
(2) binder is mixed with solvent, obtained binder solution and the shaddock ped base obtained after conductive agent, the step (1)
Biomass carbon aerogel material mixes, and coating paste is obtained after mechanical agitation is uniform；
(3) coating paste obtained after the step (2) is uniformly coated on septum body close to anode one on coating machine
Side, it is dry to be modified lithium-sulfur cell dedicated diaphragm to get to the biomass carbon aeroge.
7. preparation method according to claim 6, which is characterized in that in the step (1), hydro-thermal reaction specifically include as
Lower step：Hard epidermis, stripping and slicing is gone to clean and be put into hydrothermal reaction kettle shaddock ped, 130~200 DEG C of water in air dry oven
Then 8~12h of thermal response impregnates 1~3 day in 50~80 DEG C of hot baths, remove soluble impurity, then be placed in -30~10 DEG C
After freezing 12~36h in environment, then it is placed in 12~48h of freeze-drying in vacuum freezing drying oven；Pyrolysis temperature be 600 DEG C~
1000℃。
8. preparation method according to claim 6, which is characterized in that in the step (2), solvent be ethyl alcohol, acetone and
One or more of N-Methyl pyrrolidone；The mass ratio of binder and solvent is (1~3):(10~30)；It is churned mechanically
Speed is 500~1000r/min, and mixing time is 2~5min.
9. the preparation method according to any one of claim 6~8, which is characterized in that in the step (3), dry temperature
Degree is 20~40 DEG C, and drying time is 12~48h.
10. a kind of lithium-sulfur cell, including anode, cathode, electrolyte and diaphragm, which is characterized in that the diaphragm is claim 1
It is modified lithium described in any one of~5 or by the biomass carbon aeroge that any one of claim 6~9 preparation method is prepared
Sulphur battery dedicated diaphragm, described just extremely carbon sulphur anode composite, the cathode are metal lithium sheet, and the electrolyte includes 1,3- bis-
The mixture of butyl oxide link and glycol dimethyl ether, bis trifluoromethyl sulfonic acid Asia amide lithium and lithium nitrate.
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| CN111403659A (en) * | 2020-03-18 | 2020-07-10 | 中国科学技术大学 | Ultrahigh-specific-surface-area carbon aerogel coating diaphragm intermediate layer for lithium-sulfur battery, preparation method of ultrahigh-specific-surface-area carbon aerogel coating diaphragm intermediate layer and lithium-sulfur battery |
| CN111785912A (en) * | 2019-04-03 | 2020-10-16 | 中南大学 | Preparation method of novel porous carbon cathode lithium-sulfur battery |
| CN111785892A (en) * | 2019-04-03 | 2020-10-16 | 中南大学 | Preparation method of lithium-sulfur battery composite diaphragm |
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| CN111403659A (en) * | 2020-03-18 | 2020-07-10 | 中国科学技术大学 | Ultrahigh-specific-surface-area carbon aerogel coating diaphragm intermediate layer for lithium-sulfur battery, preparation method of ultrahigh-specific-surface-area carbon aerogel coating diaphragm intermediate layer and lithium-sulfur battery |
| CN113782912A (en) * | 2021-09-15 | 2021-12-10 | 电子科技大学长三角研究院(湖州) | Composite diaphragm modified by rhizopus hypha carbon and preparation method and application thereof |
| CN114566754A (en) * | 2022-01-24 | 2022-05-31 | 西安理工大学 | Iron-based biomass carbon composite diaphragm, preparation method thereof and lithium-sulfur battery based on iron-based biomass carbon composite diaphragm |
| CN115117551A (en) * | 2022-07-22 | 2022-09-27 | 西北工业大学深圳研究院 | High-safety functional diaphragm of lithium-sulfur battery and preparation method thereof |
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