CN110518244A - Lithium-sulfur cell binder and its preparation, application method and lithium-sulfur cell - Google Patents
Lithium-sulfur cell binder and its preparation, application method and lithium-sulfur cell Download PDFInfo
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- CN110518244A CN110518244A CN201910642354.9A CN201910642354A CN110518244A CN 110518244 A CN110518244 A CN 110518244A CN 201910642354 A CN201910642354 A CN 201910642354A CN 110518244 A CN110518244 A CN 110518244A
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
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Abstract
The present invention relates to lithium battery adhesive techniques field, a kind of lithium-sulfur cell binder and its preparation, application method and lithium-sulfur cell are specifically provided.The lithium-sulfur cell binder is chitosan acetamide urea；And/or the polymer to be formed is reacted with cross-linking agents for chitosan acetamide urea.Binder of the invention shows very strong adsorption capacity to lithium sulfide, it can inhibit the shuttle effect of sulphur anode well, and the load capacity of sulphur can be improved, so that lithium sulphur anode is more firm in lithium-sulfur cell cyclic process, to improve the electrochemistry of lithium-sulfur cell.
Description
Technical field
The invention belongs to lithium battery adhesive techniques fields, and in particular to a kind of lithium-sulfur cell binder and its preparation make
With method and lithium-sulfur cell.
Background technique
Lithium-sulfur cell has high theoretical energy density, and the specific discharge capacity and volume energy density of sulphur anode are respectively
1675mAh/g, 2800Wh/L are the several times of part commercial Li-ion battery (such as cobalt acid lithium, LiFePO4) positive electrode.Cause
And there is huge application prospect, still, lithium-sulfur cell is in charge and discharge process, the lithium sulfide of sulphur active material reduction generation
Meeting is dissolved in the electrolytic solution, is spread, and is generated " shuttle effect ", and the decaying of the continuous loss and coulombic efficiency of active material is caused.
In addition, the conductivity of redox products sulphur and lithium sulfide is also very low in sulphur anode, once losing the connection of conductive agent will lose
Remove electro-chemical activity.Revert to lithium sulfide from elemental sulfur, and reoxidize it is right in the solid-liquid-solid phase change procedure for return to sulphur simple substance
Sulphur anode causes violent structural impact, so that the specific capacity of electrode reduces to which cycle life shortens, thus from practical quotient
Industryization is applied to be needed to solve there are also problems.
Important component of the binder as lithium-sulfur cell also functions to key effect to electrode overall structure stability,
It can be effectively improved it by adjusting the chemical structure of sulphur anode bonding and adsorb lithium sulfide ability, adhesive property and flexible
Property, and the energy density of sulphur anode is promoted in turn, so that lithium-sulfur cell is in high load, under the long circulating period can still keep steady
Fixed chemical property.Kynoar is applied to pass because it has basic adhesive property and wider electrochemical window
In the lithium-sulfur cell of system, however, since this binder has weaker mechanical strength and adhesive property, so that sulphur load capacity increases
Adding the overall structure of rear electrode can not stablize, and its non-functionalized segmented structure can not inhibit sulphur anode in charge and discharge process
The shuttle effect of generation, this causes the energy density of lithium-sulfur cell and cycle performance to be unable to get raising.In addition, Kynoar
As binder in slurry preparation process, using having virose organic solvent, it is unfavorable for environmental-friendly lithium-sulfur cell
Exploitation.
Summary of the invention
For binder in current lithium-sulfur cell since mechanical strength and adhesive property are weak, electrode after sulphur load capacity increase
Integrally-built stability is poor, and its non-functionalized segmented structure can not inhibit what sulphur anode generated in charge and discharge process to wear
Shuttle effect, leads to the energy density and poor circulation of lithium-sulfur cell, and the present invention provides a kind of lithium-sulfur cell binder
And preparation method thereof.
Further, the present invention also provides with the application method of lithium-sulfur cell binder of the present invention and include the binder
Lithium-sulfur cell.
For achieving the above object, technical scheme is as follows:
A kind of lithium-sulfur cell binder, the lithium-sulfur cell binder are chitosan acetamide urea；
And/or the polymer to be formed is reacted with cross-linking agents for chitosan acetamide urea.
Correspondingly, a kind of preparation method of lithium-sulfur cell binder, comprising the following steps:
Step S01. will be mixed in semicarbazide hydrochloride and the methylene chloride under potassium carbonate addition condition of ice bath, and it is anti-to obtain first
Solution is answered, keeping the temperature of first reaction solution is (0~5) DEG C, and the dichloromethane solution of hydrochloric acid acryloyl chloride is added,
Room temperature reaction obtains reaction product to terminating；The reaction product is cleaned using ether, adjusts pH to 6~7, then
It is freeze-dried, and is cleaned, recrystallized using alcohol liquid, obtain acrylamide urea；
The acrylamide urea that step S01 is obtained is made after solution and mixes with the acid solution of chitosan by step S02., adds
Enter the base catalysis agent solution that pH value is 5~7, reacts under conditions of temperature is (55~75) DEG C to terminating, then concentrated,
It dialyses, be dried to obtain chitosan acetamide urea.
And the application method of above-mentioned lithium-sulfur cell binder, by chitosan acetamide urea and sulphur carbon complex according to matter
Amount then applies the anode sizing agent than being that the ratio of 6~10:90~94 carries out mixing, and lithium-sulphur cell positive electrode slurry is made
It is overlying on collector, obtains lithium-sulphur cell positive electrode；
Or chitosan acetamide urea, sulphur carbon complex are subjected to mixing according to the ratio that mass ratio is 6~9.5:90, and
The crosslinking agent for accounting for the chitosan acetamide urea mass ratio 0.5~4 is added, makes to be cross-linked in situ reaction, obtains lithium sulphur electricity
The anode sizing agent is then coated on collector, obtains lithium-sulphur cell positive electrode by pond anode sizing agent.
Further, a kind of lithium-sulfur cell, including anode, the just extremely lithium-sulfur cell binder as described above make
The lithium-sulphur cell positive electrode obtained with method.
Technical effect of the invention are as follows:
Compared with the existing technology, the present invention is bonded using the chitosan acetamide urea with functional side as lithium-sulfur cell
Agent, since it has abundant amide groups, hydrogen bond action forms hydrogen bond network around sulphur positive electrode between capable of playing multiple molecular
Structure, promotes the mechanical strength of polymer protective layer, and amide is as a group rich in lone pair electrons, to lithium sulfide table
Reveal very strong adsorption capacity, enhances the ability that chitosan acetamide urea inhibits shuttle effect in sulphur anode well；Or
Person is reacted so that ionomer in situ occurs with chitosan acetamide urea by crosslinking agent, is formed in situ on the interface of active material
A kind of polymer of three-dimensional net structure, three-dimensional cross-linked polymer binder can be closely by electrode materials and carbon fiber collection
Fluid adherency is got up, and effectively improves the load capacity of sulphur, while this three-dimensional cross-linked polymer makes lithium-sulfur cell cyclic process
Middle sulphur anode is more firm, to improve the electrochemistry of lithium-sulfur cell.
The preparation method of lithium-sulfur cell binder of the present invention, makes chitosan and propylene by way of mikey addition reaction
The reaction of amide urea generates chitosan acetamide urea, and the acetamide urea that the chitosan acetamide urea of acquisition has abundant amide groups can
Hydrogen bond action forms hydrogen bond network structure around sulphur positive electrode between playing multiple molecular, and the mechanics for promoting polymer protective layer is strong
Degree, and amide shows very strong adsorption capacity to lithium sulfide as a group rich in lone pair electrons, increases well
Strong chitosan acetamide urea inhibits the ability of shuttle effect in sulphur anode, and entire preparation process is simple, and raw material is cheap and easy to get.
The application method of lithium-sulfur cell binder of the invention, chitosan acetamide urea is directly direct with sulphur carbon complex
Mixed pulp, and be coated with and obtain lithium-sulphur cell positive electrode on a current collector, or by chitosan acetamide urea first with sulphur carbon complex
Slurrying carries out mixing with crosslinking agent again to be cross-linked in situ chitosan acetamide urea to react to obtain polymer, so that realization is to sulphur
Carbon complex has bonds well effect, and is coated with and obtains lithium-sulphur cell positive electrode on a current collector, the lithium-sulfur cell binder
The bond effect that application method obtains lithium-sulphur cell positive electrode sulphur carbon complex is good, can inhibit the shuttle effect of sulphur anode very well.
Lithium-sulfur cell provided by the invention, the binder as used in its anode be chitosan acetamide urea and/or
The in-situ polymerization object of chitosan acetamide urea, thus lithium-sulfur cell can have higher sulphur load capacity, and electrode overall structure
Firm, energy density is high, electrochemical performance.
Detailed description of the invention
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability
For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is the nuclear magnetic resonance spectroscopy of chitosan of the present invention and chitosan acetamide urea；
Fig. 2 is to compare after different binders of the present invention are dipped in lithium sulfide solution to lithium sulfur compounds adsorption ability
Figure；
Fig. 3 is to vulcanize after different binders of the present invention are dipped in lithium sulfide solution to the lithium after lithium sulfur compounds adsorption
Object solution is to ultraviolet visible abosrption spectrogram；
Fig. 4 is the SEM figure of the sulphur anode of the embodiment of the present invention 2；
Fig. 5 is peel test force schematic device of the present invention；
Fig. 6 is the peel test data that the sulphur anode of different binder preparations of the present invention is 1cm in sulphur anode width；
Fig. 7 is the cyclic curve and coulombic efficiency figure of the corresponding lithium-sulfur cell of the different binders of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, not
For limiting the present invention.
An aspect of of the present present invention provides a kind of preparation method of lithium-sulfur cell binder.The system of the lithium-sulfur cell binder
Preparation Method the following steps are included:
Semicarbazide hydrochloride and potassium carbonate are added in the methylene chloride under condition of ice bath step S01., mix, and obtain first
Reaction solution, keeping the temperature of first reaction solution is (0~5) DEG C, and the methylene chloride that hydrochloric acid acryloyl chloride is added is molten
Liquid, room temperature reaction obtain reaction product to terminating；The reaction product is cleaned using ether, the production after adjustment cleaning
Object pH to 6~7, is then freeze-dried, and is cleaned, recrystallized using alcohol liquid, and acrylamide urea is obtained；
The acrylamide urea that step S01 is obtained is made after solution and mixes with the acid solution of chitosan by step S02., adds
Enter the base catalysis agent solution that pH value is 5~7, reacts under conditions of temperature is (55~75) DEG C to terminating, then concentrated,
It dialyses, be dried to obtain chitosan acetamide urea.
The chitosan acetamide urea that above-mentioned preparation method obtains can be directly as lithium-sulfur cell binder, can also be with friendship
Connection agent be cross-linked in situ after reaction as lithium-sulfur cell binder.When directly being glued using chitosan acetamide urea as lithium-sulfur cell
When tying agent, since chitosan acetamide urea has functional side abundant, acetamide urea therein has acetyl ammonia abundant
Base can play hydrogen bond action between multiple molecular, and hydrogen bond network structure is formed around sulphur positive electrode, promote polymer protective layer
Mechanical strength；And amide shows very strong adsorption capacity to lithium sulfide as a group rich in lone pair electrons,
It can be very good the ability that enhancing chitosan acetamide urea inhibits sulphur anode shuttle effect.And works as chitosan acetamide urea and hand over
Connection agent carries out being cross-linked in situ reaction when being re-used as binder, can form a kind of polymer of three-dimensional net structure, three-dimensional cross-linked
Polymeric binder can closely get up electrode material and the adherency of carbon fiber collector, to be conducive to improve lithium-sulfur cell
Electrochemical stability in cyclic process.
The crosslinking agent used can be any one of polyphosphoric acids, Quadrafos, aldehyde crosslinking agent.Wherein, polyphosphoric acid
Salt can be selected from ammonium polyphosphate；Aldehyde crosslinking agent can be selected from any one of glutaraldehyde, glyoxal.
Preferably, crosslinking agent is polyphosphoric acids, and polyphosphoric acids also has lithium sulfide excellent not only as crosslinking agent
Adsorption capacity, be conducive to improve lithium sulfide stability.
In above-mentioned steps S01, according to molar ratio, semicarbazide hydrochloride using semicarbazides as measurement unit, hydrochloric acid acryloyl chloride with
Acryloyl chloride is that the preferred ingredient proportion of measurement unit, then semicarbazides and acryloyl chloride is (1~5): (1~5).In order to better
It dissolves and methylene chloride is avoided to volatilize, during semicarbazide hydrochloride and hydrochloric acid acryloyl chloride are dissolved in methylene chloride, answer
When guaranteeing methylene chloride under condition of ice bath, during avoiding hydrochloric acid acryloyl chloride that methylene chloride is added, temperature is rapidly risen
Hydrochloric acid acryloyl chloride, can be divided into multiple addition by height, each additional amount should control be added after methylene chloride temperature not
Higher than 5 DEG C, if being higher than 5 DEG C, stops that hydrochloric acid acryloyl chloride is added immediately, be further continued for that salt is added when temperature is fallen after rise to 0~5 DEG C
Acid propylene acyl chlorides.In view of controlling temperature, can be added dropwise according to the speed per minute that 30~60mmol hydrochloric acid acryloyl chloride is added dropwise
Hydrochloric acid acryloyl chloride.The additional amount of potassium carbonate can slightly be in excess in semicarbazide hydrochloride, such as according to molar ratio, semicarbazide hydrochloride with
Semicarbazides is metering, semicarbazides: potassium carbonate=(1~5): (8~16).In addition, potassium carbonate can be added as a solution, with
Improve solute effect.
Reaction product is cleaned using ether, mainly removes organic phase therein, can be cleaned multiple times, to ensure
Organic phase removal is clean.By removing the reaction product of organic phase, wherein the ether contained can realize volatilization in a vacuum.
The adjusting of pH value can be adjusted repeatedly using sodium hydroxide and hydrochloric acid, to ensure pH value 6~7.For clear
The alcohol liquid washed can be methanol or ethyl alcohol.In order to quickly remove methanol or ethyl alcohol, can be distilled by the way of revolving.
It by distillation and concentration, is recrystallized at -3~5 DEG C, obtains acrylamide urea.And in order to enable obtained acrylamide urea
Dry moisture-free, can in a vacuum be dried obtained acrylamide urea.
In step S02, acrylamide urea can be dissolved in formation acrylamide urea solution in ultrapure water.The acidity of chitosan
It is 2~3 that solution, which refers to that the pH value in the solution reaches,.Chitosan can be generally dissolved in jointly with acetic acid or hydrochloric acid or sulfuric acid ultrapure
It in water, is stirred until homogeneous with the mixing speed of 800~1400rpm, it is ensured that the chitosan solution pH value of formation reaches 2~3.
If the addition excessive velocities of basic catalyst, will lead to system pH and sharply increase, chitosan is analysed from solution
It precipitates out, reaction can not continue.Basic catalyst first can be dissolved in formation base catalysis agent solution in ultrapure water, and added
Enter vinegar acid for adjusting pH value and reach 5~7, is then added several times in the mixed solution of acrylamide urea and chitosan, base catalysis
The rate of addition of agent solution is 10-40mL per minute.
Preferably, basic catalyst is any one of triethylamine, Sodamide, sodium ethoxide.
Preferably, according to molar ratio, the ingredient proportion of chitosan and acrylamide urea is (1~5): (2~10), will be described
When chitosan solution is added in the acrylamide urea solution, revolving speed 500-1000rpm is kept to be stirred continuously, to improve dissolution speed
Degree.
It can then be dialysed using cellulose dialysis bag, thoroughly by the way of vacuum distillation or revolving when concentration
Analysis 18~for 24 hours, it can repeatedly dialyse to improve dialysis-effect, the molecular weight retained in bag filter is 10~50,000 dongles
, dialysis terminates distill solution, be lyophilized, and obtains chitosan acetamide urea.
Second aspect, the present invention provide the application method of lithium-sulfur cell binder obtained by the above method.
Specifically, the chitosan acetamide urea of above-mentioned acquisition is gathered shell when being directly used as lithium-sulfur cell binder
Sugared acetamide urea be dissolved in mass fraction be 0.5~2.0% acetum in, obtain chitosan acetamide urea solution, then with
Sulphur carbon complex carries out mixing and slurry is made, wherein the mass ratio of sulphur carbon complex and chitosan acetamide urea is 90~94:
6~10, on the carbon cloth (as collector) after being coated on hydrophilic treated, by being dried to obtain lithium-sulphur cell positive electrode.
And if with crosslinking agent carry out cross-linking reaction be re-used as lithium-sulfur cell binder when, it is first that chitosan acetamide urea is molten
In mass fraction be 0.5~2.0% acetum in, obtain chitosan acetamide urea solution, then with sulphur carbon complex into
Slurry is made in row mixing, adds crosslinking agent and carries out being cross-linked in situ reaction, so that obtaining has three-dimensional cross-linked polymer network viscous
The sulphur anode sizing agent of agent is tied, on the carbon cloth after slurry to be then coated on to hydrophilic treated, lithium-sulphur cell positive electrode can be obtained.
Chitosan acetamide urea in slurry, sulphur carbon complex, crosslinking agent mass ratio be (6~9.5): 90:(0.5~4).It will hand over
Before connection agent is mixed with slurry, crosslinking agent can be dissolved in ultrapure water, cross-linking agent solution be formed, to improve mixed effect.
In addition, the use of crosslinking agent of the invention, can also be chitosan acetamide urea being divided into two parts, wherein one
Divide chitosan acetamide urea to react with crosslinking agent and carry out mixing with sulphur carbon complex and slurry is made, it is ensured that crosslinking agent is complete
It reacts, then in the slurry that remaining part chitosan acetamide urea is added, is uniformly mixed, so that containing simultaneously in slurry
Chitosan acetamide urea binder and chitosan acetamide urea are cross-linked in situ the three-dimensional cross-linked polymer polymerizeing with crosslinking agent
Binder, then the slurry comprising two kinds of binders is coated on to the carbon cloth (as collector) after hydrophilic treated, dry
To lithium-sulphur cell positive electrode.
Above-mentioned carbon cloth is due to having flexibility, thus manufactured lithium-sulphur cell positive electrode belongs to flexible electrode.The present invention
Lithium-sulfur cell binder can also be mixed together with sulphur anode after non-flexible electrode is made.
The sulphur carbon complex being related to is to be mixed with sublimed sulfur and conductive additive, and wherein sublimed sulfur adds with conduction
The mass ratio for adding agent is 2:1, and after sublimed sulfur is mixed with conductive additive, 9~12h of heated at constant temperature at 155 DEG C obtains sulphur carbon
Compound.And conductive additive can be acetylene black, Super P, Super S, 350G, carbon fiber (VGCF), carbon nanotube
(CNTs), the carbon black materials such as Ketjen black.
The third aspect, the present invention also provides a kind of lithium-sulfur cells.
The lithium-sulfur cell includes lithium-sulphur cell positive electrode, diaphragm and lithium-sulfur cell cathode, wherein lithium-sulphur cell positive electrode is upper
The lithium-sulphur cell positive electrode that the invention of second aspect obtains is stated, diaphragm can be ceramic diaphragm, be also possible to olefines diaphragm, specifically
Olefines diaphragm can be polypropylene diaphragm, polyethylene diagrams etc., such as can be Celgard company production polypropylene diaphragm
2400；Lithium-sulfur cell cathode is metal lithium sheet.
When assembling lithium-sulfur cell, it is dissolved in 1 with 1.0M bis trifluoromethyl sulfimide lithium and 0.5~2.0% lithium nitrate,
2- dimethoxy-ethane and 1,3-dioxolane mixed solution are that electrolyte carries out fluid injection, and reservoir quantity is conventional lithium-sulfur cell electrolysis
Liquid reservoir quantity.
More effectively to illustrate technical solution of the present invention, technology of the invention is illustrated below by multiple specific embodiments
Scheme.
Embodiment 1
A kind of preparation method and lithium-sulfur cell of lithium-sulfur cell binder.The wherein preparation method packet of lithium-sulfur cell binder
Include following steps:
S11., the solution of potassium carbonate of 20mmol semicarbazide hydrochloride and 35mL 2mol/L are added to the 24mL dichloromethane in ice bath
Alkane is uniformly mixed, and obtains amino urea solution.Simultaneously keep about 0 DEG C, be stirred continuously under, by 80mmol hydrochloric acid acryloyl chloride with
24mL methylene chloride is added the speed of 30mmol is added dropwise per minute, obtains acryloyl chloride solution, the acryloyl chloride of acquisition is molten
Liquid is mixed with amino urea solution, and entire mixed solution stirs 4h in room temperature, after reaction terminates, using ether by mixture
Cleaning is transferred in vacuum tank, remaining ether volatilizees completely in a vacuum three times to remove organic phase.Then sodium hydroxide is used
It is freeze-dried after being adjusted to neutrality with hydrochloric acid solution, the product again with methanol cleaning solution obtained after freeze-drying.Revolving removes
Mixture is recrystallized at 0 DEG C, and obtains acrylamide urea after being dried in a vacuum by remaining methanol.
S12. 15mmol chitosan is added in 150mL aqueous acetic acid, is stirred by revolving speed 1400rpm to disperse
It is even, obtain chitosan solution；30mmol acrylamide urea is dissolved in formation acrylamide urea solution in 20mL ultrapure water simultaneously,
The chitosan solution is added in the acrylamide urea solution, keeps revolving speed 600rpm stirring to be uniformly mixed.It will
50mmol triethylamine is dissolved in 40mL ultrapure water, and acetic acid is added dropwise and is adjusted to neutrality, and then will prepare the triethylamine solution completed
It is added in the mixed solution of aforementioned chitosan solution and acrylamide urea solution with the speed of 20mL solution per minute, keeps turning
Fast 900rpm stirring is to be uniformly mixed.After being added dropwise to complete, solution is warming up to 60 DEG C, reacts 12h.After reaction, by solution
Concentrated by rotary evaporation, and dialysed for 24 hours using cellulose dialysis bag.It is poly- to obtain shell after rotating, being lyophilized for solution after the completion of dialysis
Sugared acetamide urea.
The chitosan acetamide urea being prepared using embodiment 1 is assembled into lithium-sulfur cell as binder:
(1) after mixes sublimed sulfur and Ketjen black according to the ratio that mass ratio is 2:1 at 155 DEG C heated at constant temperature 9h, obtain
To sulphur carbon complex.
(2) the chitosan acetamide urea is dissolved in the acetum that mass fraction is 0.5% by, and according to quality
Than for sulphur carbon complex: chitosan acetamide urea is that 90:10 prepares slurry, obtains sulphur anode sizing agent.By sulphur anode sizing agent drop coating
Onto the carbon cloth by hydrophily processing, lithium-sulfur cell sulphur anode is obtained after drying.(3) is based on above-mentioned lithium sulphur electricity
Pond anode, using lithium metal as cathode, diaphragm is the polypropylene diaphragm 2400 of Celgard company, and electrolyte composition is that 1.0M is bis-
Lithium trifluoromethanesulp,onylimide and 1.0% lithium nitrate are dissolved in 1,2- dimethoxy-ethane and 1,3-dioxolane mixed solution,
Wherein every milligram of sulphur load capacity adds 8 μ L electrolyte.Lithium-sulfur cell is prepared and carries out electro-chemical test.It is surveyed by 10 repetitions
Examination, the lithium-sulfur cell is in sulphur load capacity 6mg/cm2, current density 2mA/cm2Capacity after lower 250 circle of constant current charge-discharge circulation
Conservation rate is 63.7%.
Embodiment 2
A kind of preparation method and lithium-sulfur cell of lithium-sulfur cell binder.The wherein preparation method packet of lithium-sulfur cell binder
Include following steps:
S21., the solution of potassium carbonate of 30mmol semicarbazide hydrochloride and 50mL 2mol/L are added to the 40mL dichloromethane in ice bath
Alkane is uniformly mixed, and obtains amino urea solution.In the case where being kept for about 0 DEG C, being stirred continuously, by 100mmol hydrochloric acid acryloyl chloride with every point
40mL methylene chloride is added in the speed that 60mmol is added dropwise in clock, acryloyl chloride solution is obtained, by the acryloyl chloride solution and ammonia of acquisition
5h is stirred at room temperature in the mixing of base urea solution, entire solution again.Reaction terminate after, using ether by mixture clean three times with
Organic phase is removed, and remaining ether volatilizees completely in a vacuum.Then after being adjusted to neutrality with sodium hydroxide and hydrochloric acid solution
Freeze-drying, the product obtained after freeze-drying use ethyl alcohol cleaning solution again.Revolving removes remaining ethyl alcohol, by mixture 0
It is recrystallized at DEG C, and obtains acrylamide urea after being dried in a vacuum.
S22. 25mmol chitosan is added in 300mL aqueous acetic acid, is stirred with the revolving speed of 800rpm to be uniformly dispersed.
60mmol acrylamide urea is dissolved in after forming solution in 30mL ultrapure water, is added in chitosan solution, keeps 900rpm's
Revolving speed stirring is to be uniformly mixed.80mmol triethylamine is dissolved in 60mL ultrapure water, and acetic acid is added dropwise and adjusts to neutrality, then will
The triethylamine solution for preparing completion is added to aforementioned chitosan solution with the speed of 10mL solution per minute and acrylamide urea is molten
In the mixed solution of liquid, keep revolving speed 500rpm stirring to be uniformly mixed.After being added dropwise to complete, solution is warming up to 70 DEG C, reaction
12h.After reaction, it by solution concentrated by rotary evaporation, and is dialysed for 24 hours using cellulose dialysis bag.Solution passes through after the completion of dialysis
Chitosan acetamide urea is obtained after crossing revolving, freeze-drying.
The chitosan acetamide urea being prepared using embodiment 2 is assembled into lithium-sulfur cell as binder:
(1) by sublimed sulfur and Ketjen black according to mass ratio be after 2:1 is mixed at 155 DEG C heated at constant temperature 10h, obtain sulphur
Carbon complex.
(2) the chitosan acetamide urea is dissolved in the acetum that mass fraction is 0.5% by, and according to quality
Than for sulphur carbon complex: chitosan acetamide urea is that 90:9 prepares slurry, is sulphur carbon complex: chitosan second according still further to mass ratio
Amide urea: polyphosphoric acids=90:9:1 ratio is added poly phosphoric acid solution and carries out being cross-linked in situ reaction, obtains handing over based on three-dimensional
The sulphur anode sizing agent of linked polymer network binder；By slurry drop coating to passing through on the carbon cloth of hydrophily processing, through overdrying
Lithium-sulfur cell sulphur anode is obtained after dry.
(3) is based on above-mentioned lithium sulphur anode, and using lithium metal as cathode, diaphragm is the polypropylene diaphragm of Celgard company
2400, electrolyte composition is that 1.0M bis trifluoromethyl sulfimide lithium and 1.0% lithium nitrate are dissolved in 1,2- dimethoxy-ethane
With 1,3-dioxolane mixed solution, wherein every milligram of sulphur load capacity adds 8 μ L electrolyte.By 10 retests, the lithium
Sulphur battery is in sulphur load capacity 6mg/cm2, current density 2mA/cm2Capacity retention ratio after 250 circle of lower constant current charge-discharge circulation is
81.6%.
Embodiment 3
A kind of preparation method and lithium-sulfur cell of lithium-sulfur cell binder.The wherein preparation method packet of lithium-sulfur cell binder
Include following steps:
S31., 40mmol semicarbazide hydrochloride and 75mL 2mol/L solution of potassium carbonate are added to the 50mL dichloromethane in ice bath
Alkane is uniformly mixed, and obtains amino urea solution.In the case where being kept for about 0 DEG C, being stirred continuously, by 150mmol hydrochloric acid acryloyl chloride with every point
50mL methylene chloride is added in the speed that 40mmol is added dropwise in clock, acryloyl chloride solution is obtained, by the acryloyl chloride solution and ammonia of acquisition
5h is stirred at room temperature in the mixing of base urea solution, entire solution again.Reaction terminate after, using ether by mixture clean three times with
Organic phase is removed, and remaining ether volatilizees completely in a vacuum.Then after being adjusted to neutrality with sodium hydroxide and hydrochloric acid solution
Freeze-drying, the product obtained after freeze-drying use ethyl alcohol cleaning solution again.Revolving removes remaining ethyl alcohol, by mixture 0
It is recrystallized at DEG C, and obtains acrylamide urea after being dried in a vacuum.
S32. 40mmol chitosan is added in 400mL aqueous acetic acid, is that 900rpm is stirred to disperse by revolving speed
It is even.80mmol acrylamide urea is dissolved in after forming solution in 50mL ultrapure water, is added in chitosan solution, keeps revolving speed
800rpm stirring is to be uniformly mixed.120mmol triethylamine is dissolved in 50mL ultrapure water, and acetic acid is added dropwise and adjusts to neutrality, so
The triethylamine solution completed will be prepared afterwards, and aforementioned chitosan solution and acrylamide are added to the speed of 30mL solution per minute
In the mixed solution of urea solution, keep revolving speed 600rpm stirring to be uniformly mixed.After being added dropwise to complete, solution is warming up to 70 DEG C,
React 12h.After reaction, it by solution concentrated by rotary evaporation, and is dialysed for 24 hours using cellulose dialysis bag.It is molten after the completion of dialysis
Liquid obtains chitosan acetamide urea after rotating, being lyophilized.
The chitosan acetamide urea being prepared using embodiment 3 is assembled into lithium-sulfur cell as binder:
(1) sublimed sulfur and Ketjen black according to mass ratio be after 2:1 is mixed at 155 DEG C heated at constant temperature 11h, obtain sulphur carbon
Compound.
(2) the chitosan acetamide urea is dissolved in the acetum that mass fraction is 0.5% by, and according to quality
Than for sulphur carbon complex: chitosan acetamide urea is that 90:8 prepares slurry, is sulphur carbon complex: chitosan second according still further to mass ratio
Amide urea: polyphosphoric acids=90:8:2 ratio is added poly phosphoric acid solution and carries out being cross-linked in situ reaction, obtains handing over based on three-dimensional
The sulphur anode sizing agent of linked polymer network binder；By slurry drop coating to passing through on the carbon cloth of hydrophily processing, through overdrying
Lithium-sulfur cell sulphur anode is obtained after dry.
(3) is based on above-mentioned lithium sulphur anode, and using lithium metal as cathode, diaphragm is the polypropylene diaphragm of Celgard company
2400, electrolyte composition is that 1.0M bis trifluoromethyl sulfimide lithium and 1.0% lithium nitrate are dissolved in 1,2- dimethoxy-ethane
With 1,3-dioxolane mixed solution, wherein every milligram of sulphur load capacity adds 8 μ L electrolyte.By 10 retests, the lithium
Sulphur battery is in sulphur load capacity 6mg/cm2, current density 2mA/cm2Capacity retention ratio after 250 circle of lower constant current charge-discharge circulation is
80.9%.
Embodiment 4
A kind of preparation method and lithium-sulfur cell of lithium-sulfur cell binder.The wherein preparation method packet of lithium-sulfur cell binder
Include following steps:
S41., the solution of potassium carbonate of 50mmol semicarbazide hydrochloride and 80mL 2mol/L are added to the 70mL dichloromethane in ice bath
Alkane is uniformly mixed, and obtains amino urea solution.In the case where being kept for about 0 DEG C, being stirred continuously, by 200mmol hydrochloric acid acryloyl chloride with every point
70mL methylene chloride is added in the speed that 50mmol is added dropwise in clock, acryloyl chloride solution is obtained, by the acryloyl chloride solution and ammonia of acquisition
6h is stirred at room temperature in the mixing of base urea solution, entire solution again.Reaction terminate after, using ether by mixture clean three times with
Organic phase is removed, and remaining ether volatilizees completely in a vacuum.Then after being adjusted to neutrality with sodium hydroxide and hydrochloric acid solution
Freeze-drying, the product obtained after freeze-drying use ethyl alcohol cleaning solution again.Revolving removes remaining ethyl alcohol, by mixture 0
It is recrystallized at DEG C, and obtains acrylamide urea after being dried in a vacuum.
S42. 50mmol chitosan is added in 500mL aqueous acetic acid, is that 1000rpm is stirred to disperse by revolving speed
It is even.100mmol acrylamide urea is dissolved in after forming solution in 80mL ultrapure water, is added in chitosan solution, keeps revolving speed
1000rpm stirring is to be uniformly mixed.100mmol triethylamine is dissolved in 100mL ultrapure water, and acetic acid is added dropwise and adjusts to neutrality,
Then the triithylamine solution completed will be prepared, aforementioned chitosan solution and acryloyl is added to the speed of 40mL solution per minute
In the mixed solution of amine urea solution, keep revolving speed 1000rpm stirring to be uniformly mixed.After being added dropwise to complete, solution is warming up to 70
DEG C, react 12h.After reaction, it by solution concentrated by rotary evaporation, and is dialysed for 24 hours using cellulose dialysis bag.After the completion of dialysis
Solution obtains chitosan acetamide urea after rotating, being lyophilized.
The chitosan acetamide urea being prepared using embodiment 4 is assembled into lithium-sulfur cell as binder:
(1) by sublimed sulfur and Ketjen black according to mass ratio be after 2:1 is mixed at 155 DEG C heated at constant temperature 12h, obtain sulphur
Carbon complex.
(2) the chitosan acetamide urea is dissolved in the acetum that mass fraction is 0.5% by, and according to quality
Than for sulphur carbon complex: chitosan acetamide urea is that 90:6 prepares slurry, is sulphur carbon complex: chitosan second according still further to mass ratio
Amide urea: polyphosphoric acids=90:6:4 ratio is added poly phosphoric acid solution and carries out being cross-linked in situ reaction, obtains handing over based on three-dimensional
The sulphur anode sizing agent of linked polymer network binder；By slurry drop coating to passing through on the carbon cloth of hydrophily processing, through overdrying
Lithium-sulfur cell sulphur anode is obtained after dry.
(3) is based on lithium sulphur anode, and using lithium metal as cathode, diaphragm is the polypropylene diaphragm 2400 of Celgard company,
Electrolyte composition is that 1.0M bis trifluoromethyl sulfimide lithium and 1.0% lithium nitrate are dissolved in 1,2- dimethoxy-ethane and 1,3-
Dioxolanes mixed solution, wherein every milligram of sulphur load capacity adds 8 μ L electrolyte.By 10 retests, the lithium-sulfur cell
In sulphur load capacity 6mg/cm2, current density 2mA/cm2Capacity retention ratio after 250 circle of lower constant current charge-discharge circulation is
76.9%.
Embodiment 5
A kind of preparation method and lithium-sulfur cell of lithium-sulfur cell binder.The wherein preparation method packet of lithium-sulfur cell binder
Include following steps:
S51., the solution of potassium carbonate of 50mmol semicarbazide hydrochloride and 80mL 2mol/L are added to the 70mL dichloromethane in ice bath
Alkane is uniformly mixed, and obtains amino urea solution.In the case where being kept for about 0 DEG C, being stirred continuously, by 50mmol hydrochloric acid acryloyl chloride with every point
20mL methylene chloride is added in the speed that 55mmol is added dropwise in clock, acryloyl chloride solution is obtained, by the acryloyl chloride solution and ammonia of acquisition
8h is stirred at room temperature in the mixing of base urea solution, entire solution again.Reaction terminate after, using ether by mixture clean three times with
Organic phase is removed, and remaining ether volatilizees completely in a vacuum.Then after being adjusted to neutrality with sodium hydroxide and hydrochloric acid solution
Freeze-drying, the product obtained after freeze-drying use ethyl alcohol cleaning solution again.Revolving removes remaining ethyl alcohol, by mixture 0
It is recrystallized at DEG C, and obtains acrylamide urea after being dried in a vacuum.
S52. 10mmol chitosan is added in 100mL aqueous acetic acid, is that 1200rpm is stirred to disperse by revolving speed
It is even.100mmol acrylamide urea is dissolved in after forming solution in 80mL ultrapure water, is added in chitosan solution, keeps revolving speed
500rpm stirring is to be uniformly mixed.100mmol triethylamine is dissolved in 100mL ultrapure water, and acetic acid is added dropwise and adjusts to neutrality, so
The triithylamine solution completed will be prepared afterwards, and aforementioned chitosan solution and acrylamide are added to the speed of 40mL solution per minute
In the mixed solution of urea solution, keep revolving speed 800rpm stirring to be uniformly mixed.After being added dropwise to complete, solution is warming up to 70 DEG C,
React 12h.After reaction, it by solution concentrated by rotary evaporation, and is dialysed for 24 hours using cellulose dialysis bag.It is molten after the completion of dialysis
Liquid obtains chitosan acetamide urea after rotating, being lyophilized.
The chitosan acetamide urea being prepared using embodiment 5 is assembled into lithium-sulfur cell as binder:
(1) by sublimed sulfur and Ketjen black according to mass ratio be after 2:1 is mixed at 155 DEG C heated at constant temperature 12h, obtain sulphur
Carbon complex.
(2) the chitosan acetamide urea is dissolved in the acetum that mass fraction is 0.5% by, and according to quality
Than for sulphur carbon complex: chitosan acetamide urea is that 90:6 prepares slurry, is sulphur carbon complex: chitosan second according still further to mass ratio
Amide urea: polyphosphoric acids=90:6:4 ratio is added poly phosphoric acid solution and carries out being cross-linked in situ reaction, obtains handing over based on three-dimensional
The sulphur anode sizing agent of linked polymer network binder；By slurry drop coating to passing through on the carbon cloth of hydrophily processing, through overdrying
Lithium-sulfur cell sulphur anode is obtained after dry.
(3) is based on lithium sulphur anode, and using lithium metal as cathode, diaphragm is the polypropylene diaphragm 2400 of Celgard company,
Electrolyte composition is that 1.0M bis trifluoromethyl sulfimide lithium and 1.0% lithium nitrate are dissolved in 1,2- dimethoxy-ethane and 1,3-
Dioxolanes mixed solution, wherein every milligram of sulphur load capacity adds 8 μ L electrolyte.By 10 retests, the lithium-sulfur cell
In sulphur load capacity 6mg/cm2, current density 2mA/cm2Capacity retention ratio after 250 circle of lower constant current charge-discharge circulation is
75.6%.
Embodiment 6
A kind of preparation method and lithium-sulfur cell of lithium-sulfur cell binder.The wherein preparation method packet of lithium-sulfur cell binder
Include following steps:
S61., the solution of potassium carbonate of 50mmol semicarbazide hydrochloride and 80mL 2mol/L are added to the 70mL dichloromethane in ice bath
Alkane is uniformly mixed, and obtains amino urea solution.In the case where being kept for about 0 DEG C, being stirred continuously, by 250mmol hydrochloric acid acryloyl chloride with every point
40mL methylene chloride is added in the speed that 50mmol is added dropwise in clock, acryloyl chloride solution is obtained, by the acryloyl chloride solution and ammonia of acquisition
8h is stirred at room temperature in the mixing of base urea solution, entire solution again.Reaction terminate after, using ether by mixture clean three times with
Organic phase is removed, and remaining ether volatilizees completely in a vacuum.Then after being adjusted to neutrality with sodium hydroxide and hydrochloric acid solution
Freeze-drying, the product obtained after freeze-drying use ethyl alcohol cleaning solution again.Revolving removes remaining ethyl alcohol, by mixture 0
It is recrystallized at DEG C, and obtains acrylamide urea after being dried in a vacuum.
S62. 50mmol chitosan is added in 100mL aqueous acetic acid, is that 1200rpm is stirred to disperse by revolving speed
It is even.20mmol acrylamide urea is dissolved in after forming solution in 40mL ultrapure water, is added in chitosan solution, keeps revolving speed
500rpm stirring is to be uniformly mixed.100mmol triethylamine is dissolved in 100mL ultrapure water, and acetic acid is added dropwise and adjusts to neutrality, so
The triithylamine solution completed will be prepared afterwards, and aforementioned chitosan solution and acrylamide are added to the speed of 40mL solution per minute
In the mixed solution of urea solution, keep revolving speed 800rpm stirring to be uniformly mixed.After being added dropwise to complete, solution is warming up to 70 DEG C,
React 12h.After reaction, it by solution concentrated by rotary evaporation, and is dialysed for 24 hours using cellulose dialysis bag.It is molten after the completion of dialysis
Liquid obtains chitosan acetamide urea after rotating, being lyophilized.
The chitosan acetamide urea being prepared using embodiment 6 is assembled into lithium-sulfur cell as binder:
(1) by sublimed sulfur and Ketjen black according to mass ratio be after 2:1 is mixed at 155 DEG C heated at constant temperature 12h, obtain sulphur
Carbon complex.
(2) the chitosan acetamide urea is dissolved in the acetum that mass fraction is 0.5% by, and according to quality
Than for sulphur carbon complex: chitosan acetamide urea is that 90:6 prepares slurry, is sulphur carbon complex: chitosan second according still further to mass ratio
Amide urea: polyphosphoric acids=90:6:4 ratio is added poly phosphoric acid solution and carries out being cross-linked in situ reaction, obtains handing over based on three-dimensional
The sulphur anode sizing agent of linked polymer network binder；By slurry drop coating to passing through on the carbon cloth of hydrophily processing, through overdrying
Lithium-sulfur cell sulphur anode is obtained after dry.
(3) is based on lithium sulphur anode, and using lithium metal as cathode, diaphragm is the polypropylene diaphragm 2400 of Celgard company,
Electrolyte composition is that 1.0M bis trifluoromethyl sulfimide lithium and 1.0% lithium nitrate are dissolved in 1,2- dimethoxy-ethane and 1,3-
Dioxolanes mixed solution, wherein every milligram of sulphur load capacity adds 8 μ L electrolyte.By 10 retests, the lithium-sulfur cell
In sulphur load capacity 6mg/cm2, current density 2mA/cm2Capacity retention ratio after 250 circle of lower constant current charge-discharge circulation is
78.2%.
Comparative example 1
A kind of preparation method of lithium-sulfur cell, comprising the following steps:
(1) by sublimed sulfur and Ketjen black according to mass ratio be after 2:1 is mixed at 155 DEG C heated at constant temperature 10h, obtain sulphur
Carbon complex.
(2) is sulphur carbon complex according to mass ratio: Kynoar is that 90:10 prepares slurry；By slurry drop coating to process
On the carbon cloth of hydrophily processing, lithium-sulfur cell sulphur anode is obtained after drying.
(3) is based on above-mentioned lithium sulphur anode, and using lithium metal as cathode, diaphragm is the polypropylene diaphragm of Celgard company
2400, electrolyte composition is that 1.0M bis trifluoromethyl sulfimide lithium and 1.0% lithium nitrate are dissolved in 1,2- dimethoxy-ethane
With 1,3-dioxolane mixed solution, wherein adding the sulphur of 8 μ L in every gram of electrolyte.By 10 retests, the lithium sulphur electricity
Pond is in sulphur load capacity 6mg/cm2, current density 2mA/cm2Capacity retention ratio after 175 circle of lower constant current charge-discharge circulation is
20.1%.
Comparative example 2
A kind of preparation method of lithium-sulfur cell, comprising the following steps:
(1) by sublimed sulfur and Ketjen black according to mass ratio be after 2:1 is mixed at 155 DEG C heated at constant temperature 10h, obtain sulphur
Carbon complex.
(2) is sulphur carbon complex according to mass ratio: chitosan is that 90:10 prepares slurry；By slurry drop coating to by hydrophilic
Property processing carbon cloth on, lithium-sulfur cell sulphur anode is obtained after drying.
(3) is based on above-mentioned lithium sulphur anode, and using lithium metal as cathode, diaphragm is the polypropylene diaphragm of Celgard company
2400, electrolyte composition is that 1.0M bis trifluoromethyl sulfimide lithium and 1.0% lithium nitrate are dissolved in 1,2- dimethoxy-ethane
With 1,3-dioxolane mixed solution, wherein adding the sulphur of 8 μ L in every gram of electrolyte.By 10 retests, the lithium sulphur electricity
Pond is in sulphur load capacity 6mg/cm2, current density 2mA/cm2Capacity retention ratio after 220 circle of lower constant current charge-discharge circulation is
27.0%.
In order to verify above-described embodiment 1~2 and the characteristic of material that comparative example 1~2 obtains, it is carried out below relevant
Performance test.
(1) binder nucleus magnetic hydrogen spectrum
The nucleus magnetic hydrogen spectrum that the chitosan acetamide urea that chitosan raw material and embodiment 1 are obtained carries out is tested, and specifically will
Component is dissolved in the mixed liquor that solvent is deuterated water and deuterated acetic acid respectively, as a result as shown in Figure 1.
From fig. 1, it can be seen that by the nucleus magnetic hydrogen spectrum of comparison chitosan acetamide urea and chitosan, in chemical shift 5.5-
At 5.6ppm and 4.7-4.8ppm, occur two methylene peaks being apparent in chitosan acetamide urea data, it was demonstrated that propylene
The successful progress of Michael addition reaction between amide urea and chitosan.
(2) physical absorption ability
Chitosan acetamide urea, the 2 chitosan acetamide urea of embodiment that Kynoar, chitosan, embodiment 1 are obtained
Pure electrolyte involved in reaction product, the embodiment of the present invention, which is cross-linked in situ, with polyphosphoric acids is separately added into lithium sulfide solution
(brown-red solution reacted after electrolyte, Average molecular formula Li is added in sulphur and lithium sulfide2S6), and stand what 12h was obtained
Different lithium sulfide solution photo and its UV-vis absorption spectrum are specifically detailed in Fig. 2,3.
As can be seen from Figure 2, it is cross-linked in situ what reaction product namely chitosan acetamide urea were obtained with polyphosphoric acids cross-linking reaction
Three-dimensional cross-linked binder shows strongest physical absorption ability to lithium sulfide, so that the lithium sulfide solution of brownish red is gradually
It is changed into the clear transparent solutions of intimate pure electrolyte, chitosan acetamide urea is relatively weak to the adsorption capacity of lithium sulfide,
Chitosan is weaker, and Kynoar does not then almost have adsorption capacity to lithium sulfide, also therefore can not lithium sulphur in lithium-sulfur cell
Shuttle of the compound from positive to cathode.
The UV-vis absorption spectrum of Fig. 3 shows identical variation tendency.
(3) scanning electron microscope diagram (SEM)
It is scanned using the lithium-sulphur cell positive electrode that TESCAM MIRA3 equipment obtains embodiment 2, as a result such as Fig. 4.
As can be seen from Figure 4, an overlapping ball of string is carbon cloth, and intermediate granular filler is electrode material, i.e. sulphur, conduction
The mixture of agent and binder.Electrode material is well dispersed in the hole of carbon cloth, takes full advantage of carbon cloth
Space, while being formed with carbon cloth and being closely adhered.
(4) peel test force
Using peel test force device shown in fig. 5 to Kynoar, chitosan, chitosan acetamide urea, chitosan
The lithium-sulphur cell positive electrode that acetamide urea and the product of polyphosphoric acids cross-linking reaction are prepared as binder carries out the survey of peeling force performance
Examination, specific test results are shown in figure 6.
As can be seen from Figure 6, product chitosan acetamide urea and polyphosphoric acids cross-linking reaction obtained is prepared as binder
Lithium-sulphur cell positive electrode peeling force be up to 5.1N, more than the 10 of positive (0.5N) the surveyed peeling force of the lithium sulphur based on Kynoar
Times, while chitosan acetamide urea also shows very strong peeling force, shows chitosan acetamide urea and chitosan acetyl
Amine urea and polyphosphoric acids cross-linking reaction product all have very strong adhesive capacity as binder, can be in circulating battery process
It is middle to be adhered sulphur, conductive agent sum aggregate fluid-tight, guarantee the stability of electrode structure.
(5) lithium-sulfur cell cycle performance curve
The lithium-sulfur cell that embodiment 1,2 and comparative example 1,2 are obtained carries out cycle performance test, specific test parameter
For in sulphur load capacity 6mg/cm2, current density 2mA/cm2When constant current charge-discharge loop-around data.It is real after 250 circle circulations
It applies the lithium-sulfur cell in example 2 and shows most stable of chemical property, capacity retention ratio is up to 83.5%, and coulombic efficiency is maintained at
96.4%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc. within mind and principle should all include within protection scope of the present invention.
Claims (10)
1. a kind of lithium-sulfur cell binder, which is characterized in that the lithium-sulfur cell binder is chitosan acetamide urea；
And/or the polymer to be formed is reacted with cross-linking agents for chitosan acetamide urea.
2. lithium-sulfur cell binder as described in claim 1, which is characterized in that the crosslinking agent is polyphosphoric acids, polyphosphoric acid
Any one of salt, aldehyde crosslinking agent.
3. lithium-sulfur cell binder as claimed in claim 1 or 2, which is characterized in that the chitosan acetamide urea is gathered by shell
Sugar is prepared with acrylamide urea by Michael addition reaction.
4. a kind of preparation method of lithium-sulfur cell binder, which comprises the following steps:
Step S01. will be mixed in semicarbazide hydrochloride and the methylene chloride under potassium carbonate addition condition of ice bath, and it is molten to obtain the first reaction
Liquid, keeping the temperature of first reaction solution is (0~5) DEG C, and the dichloromethane solution of hydrochloric acid acryloyl chloride, room temperature is added
Reaction obtains reaction product to terminating；The reaction product is cleaned using ether, pH to 6~7 is adjusted, then carries out
Freeze-drying, and cleaned, recrystallized using alcohol liquid, obtain acrylamide urea；
The acrylamide urea that step S01 is obtained is made after solution and mixes with the acid solution of chitosan by step S02., and pH is added
The base catalysis agent solution that value is 5~7 reacts under conditions of temperature is (55~75) DEG C to terminating, then concentrated, saturating
It analyses, be dried to obtain chitosan acetamide urea.
5. the preparation method of lithium-sulfur cell binder as claimed in claim 4, which is characterized in that according to molar ratio, and hydrochloric acid
Semicarbazides according to semicarbazides meter, hydrochloric acid acryloyl chloride according to acryloyl chloride meter, in above-mentioned reaction raw materials component, semicarbazides: propylene
Acyl chlorides=(1~5): (1~5)；
The chitosan: acrylamide urea=(1~5): (2~10).
6. the preparation method of lithium-sulfur cell binder as claimed in claim 4, which is characterized in that the acidity of the chitosan is molten
The pH value of liquid is 2~3.
7. the preparation method of lithium-sulfur cell binder as claimed in claim 4, which is characterized in that in step S02, base catalysis
Agent is selected from any one of triethylamine, Sodamide, sodium ethoxide.
8. lithium-sulfur cell binder as claimed in any one of claims 1 to 3 or the lithium sulphur as described in any one of claim 4~7
The application method for the lithium-sulfur cell binder that the preparation method of battery binder is prepared, which is characterized in that by chitosan second
Lithium-sulphur cell positive electrode slurry is made according to the ratio progress mixing that mass ratio is 6~10:90~94 in amide urea and sulphur carbon complex
The anode sizing agent is then coated on collector, obtains lithium-sulphur cell positive electrode by material；
Or chitosan acetamide urea, sulphur carbon complex are subjected to mixing according to the ratio that mass ratio is 6~9.5:90, and be added
The crosslinking agent for accounting for the chitosan acetamide urea mass ratio 0.5~4, makes to be cross-linked in situ reaction, is obtaining lithium-sulfur cell just
The anode sizing agent is then coated on collector, obtains lithium-sulphur cell positive electrode by pole slurry.
9. the application method of lithium-sulfur cell binder as claimed in claim 8, which is characterized in that the chitosan acetamide urea
It is dissolved in the acetum that mass fraction is 0.5~2.0%；
The crosslinking agent is any one of polyphosphoric acids, Quadrafos, aldehyde crosslinking agent；
The sulphur carbon complex is the mixture of sulphur and conductive additive；
The collector is hydrophilic treated carbon cloth.
10. a kind of lithium-sulfur cell, including anode, which is characterized in that the just extremely described in any item lithiums of claim 8~9
The lithium-sulphur cell positive electrode that the application method of sulphur battery binder obtains.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111697231A (en) * | 2020-05-20 | 2020-09-22 | 华南理工大学 | Natural aqueous sulfur positive electrode binder, preparation method thereof and application of binder in preparation of sulfur positive electrode of lithium-sulfur battery |
| CN112993250A (en) * | 2019-12-13 | 2021-06-18 | 南方科技大学 | Binder for lithium-sulfur battery positive electrode, sulfur positive electrode slurry, sulfur positive electrode and preparation method |
| CN116574201A (en) * | 2023-04-07 | 2023-08-11 | 大连理工大学 | Preparation method of bio-based water-based polymer binder for lithium-sulfur battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760883A (en) * | 2012-07-13 | 2012-10-31 | 中国科学院广州能源研究所 | Novel chitosan used for lithium ion cell and derivative water-based binder of chitosan |
| CN103515613A (en) * | 2013-10-02 | 2014-01-15 | 中国地质大学（武汉） | Additive for lithium-sulfur batteries and anode material containing same |
| WO2018087543A1 (en) * | 2016-11-11 | 2018-05-17 | Oxis Energy Limited | Electrode for lithium sulphur cell |
| CN108336356A (en) * | 2018-03-28 | 2018-07-27 | 广州鹏辉能源科技股份有限公司 | Positive electrode, positive plate and preparation method thereof and lithium ion battery |
| CN108649228A (en) * | 2018-03-23 | 2018-10-12 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery silicon substrate cathode binder, cathode and preparation method |
| CN109244468A (en) * | 2018-08-02 | 2019-01-18 | 合肥国轩高科动力能源有限公司 | A kind of chitosan negative electrode binder of modification and the preparation method of the negative electrode tab containing the binder |
-
2019
- 2019-07-16 CN CN201910642354.9A patent/CN110518244A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760883A (en) * | 2012-07-13 | 2012-10-31 | 中国科学院广州能源研究所 | Novel chitosan used for lithium ion cell and derivative water-based binder of chitosan |
| CN103515613A (en) * | 2013-10-02 | 2014-01-15 | 中国地质大学（武汉） | Additive for lithium-sulfur batteries and anode material containing same |
| WO2018087543A1 (en) * | 2016-11-11 | 2018-05-17 | Oxis Energy Limited | Electrode for lithium sulphur cell |
| CN108649228A (en) * | 2018-03-23 | 2018-10-12 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery silicon substrate cathode binder, cathode and preparation method |
| CN108336356A (en) * | 2018-03-28 | 2018-07-27 | 广州鹏辉能源科技股份有限公司 | Positive electrode, positive plate and preparation method thereof and lithium ion battery |
| CN109244468A (en) * | 2018-08-02 | 2019-01-18 | 合肥国轩高科动力能源有限公司 | A kind of chitosan negative electrode binder of modification and the preparation method of the negative electrode tab containing the binder |
Non-Patent Citations (1)
| Title |
|---|
| 易欢: "锂硫电池正极水性聚合物粘结剂的研究", 《中国博士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112993250A (en) * | 2019-12-13 | 2021-06-18 | 南方科技大学 | Binder for lithium-sulfur battery positive electrode, sulfur positive electrode slurry, sulfur positive electrode and preparation method |
| CN111697231A (en) * | 2020-05-20 | 2020-09-22 | 华南理工大学 | Natural aqueous sulfur positive electrode binder, preparation method thereof and application of binder in preparation of sulfur positive electrode of lithium-sulfur battery |
| CN116574201A (en) * | 2023-04-07 | 2023-08-11 | 大连理工大学 | Preparation method of bio-based water-based polymer binder for lithium-sulfur battery |
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