CN103515614B - A kind of additives for battery, positive electrode containing this additive and preparation method thereof - Google Patents
A kind of additives for battery, positive electrode containing this additive and preparation method thereof Download PDFInfo
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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 provides a kind of lithium-sulfur cell additive, and the positive electrode containing this additive and preparation method thereof, described additive product after to be material with carbon element compound with monose or the polysaccharide carbonization that is polymerized by monose, containing strong lone pair electrons group in described monose and polysaccharide.Described strong lone pair electrons group is C=O or OH.Described monose is selected from glucose, fructose, galactolipin, ribose, glycogen and deoxyribose.The conductive carbon material that positive electrode in the present invention uses has good adsorption capacity and has high-specific surface area, big pore volume, loose structure, and electroactive substance is sulphur.Additive is the material containing strong lone pair electrons group.The many lithium sulfides produced in discharge process can be formed with the modes such as coordination and additive and interact so that it is dissolving in the electrolytic solution is suppressed, and loss and the cathode of lithium burn into capacity attenuation that therefore can effectively reduce active material wait rapidly and affect.
Description
Technical field
The present invention relates to a kind of novel carbon-sulfur positive electrode being applied to lithium-sulfur cell and preparation method thereof, particularly relate to the additive of carbon sulphur positive electrode, concretely relate to the polysaccharide of the monose such as the glucose containing strong lone pair electrons group, fructose, galactolipin, ribose, deoxyribose and polymerization thereof compound with material with carbon element after the additive A that generates and the preparation method of corresponding C/S/A positive electrode, and lithium-sulfur cell based on this C/S/A positive electrode prepares, assembles and measuring technology.
Background technology
Currently, with Li2CoO2、LiFePO4Quite varied application has been obtained Deng the lithium rechargeable battery for positive electrode.But, it being limited to these positive electrode theory specific energies, existing lithium-ion battery system is difficult to meet the fields such as future portable electronic device and mobile traffic to power supply lightweight, miniaturization, low cost and avirulent demand.The research and development of the lithium secondary battery of high-energy-density have caused increasing concern, the most especially with elemental sulfur as positive pole, the lithium metal lithium-sulfur secondary battery system as negative pole be to write, the research and development about this system have become study hotspot nearly ten years.
Single sulphur positive electrode is by electrochemical reaction S8+16Li→8Li2S counts its specific capacity and is up to 1675mAh g-1, it is that in known solid positive electrode, energy density is the highest, and sulphur simple substance rich reserves, cheap, safety and low toxicity, thus there is the most wide application prospect.But, sulphur simple substance is typical electronic body (5 × 10-30S·cm-1, 25 DEG C), electro-chemical activity is poor；Electric discharge end product Li2S volumetric expansion compared with electric discharge original state reaches 87%, causes sulphur positive pole loosely organized or even destroyed in charge and discharge cycles；The lithium polysulfide Li that sulfur electrode is formed at certain level of charge2Sn(n=6～8) is soluble in electrolyte, and diffuses to lithium electrode and occur with it self discharge reaction to generate lithium polysulfide Li2Sn(n=3～4), causes lithium to corrode.Li simultaneously2Sn(n=3～4) spreads back again sulfur electrode and is oxidized to Li2SnDiffuse to lithium electrode surface after (n=6～8) again, i.e. " effect of shuttling back and forth " occurs.Effect that what the dissolving of polysulfide caused shuttle back and forth is one of difficult problem of lithium-sulfur cell most critical, significantly reduces the utilization rate of sulphur, specific capacity and cycle performance, adds the viscosity of electrolyte and the migration resistance of ion simultaneously.Along with the carrying out of discharge process, the electric discharge end product Li of poorly conductive2S and Li2S2The surface of positive electrode active materials can be covered with the form of solid film, thus hinder the electrochemical reaction between electrolyte and electrode active material.
In order to solve the problems referred to above, there has been proposed many solutions.Mainly set about in terms of improving material with carbon element, binding agent, polymer overmold, cathode of lithium modification, positive electrode additive etc..
For positive electrode, Chinese patent CN102208645A discloses a kind of amorphous carbon cladding sulphur, Chinese patent CN101986443A discloses a kind of nano hollow carbon pipe cladding sulphur, Chinese patent CN102709533A discloses a kind of graphene coated sulphur, Chinese patent CN102315424A discloses a kind of sulphur/conductive polymer nanometer pipe composite positive pole, described sulphur content dissipates in the tube-surface and the pipe that are adsorbed in described conductive polymer nanometer pipe, forms the filamentary structure of hollow.Chinese patent CN102074704A discloses the preparation method of a kind of secondary lithium-sulfur battery anode adhesive.For negative material, Chinese patent CN1508893 discloses the negative pole of a kind of lithium-sulfur cell, and described negative pole includes lithium metal, one layer of pretreatment layer and the protective layer of one layer of protection lithium metal.Chinese patent CN1503385 discloses a kind of inorganic oxide additive, and Chinese patent CN1482693A discloses a kind of polymeric additive containing ammonia nitrogen.
The above-mentioned patent for positive electrode mainly uses material with carbon element cladding, polymer overmold or nano material additive cladding sulphur etc. to improve lithium-sulfur cell cycle performance.
Summary of the invention
The invention provides a kind of new additive agent, the specific function group on a small amount of additive introduced is utilized to adsorb polysulfide, effectively to suppress polysulfide dissolving in charge and discharge process, reduce the adverse effect that effect of shuttling back and forth is brought, improve lithium-sulfur cell cycle performance.
The technical scheme realizing above-mentioned purpose is:
A kind of additive being applied in lithium-sulfur cell, described additive product after to be material with carbon element compound with monose or the polysaccharide carbonization that is polymerized by monose, containing strong lone pair electrons group in described monose and polysaccharide.Described strong lone pair electrons group is-C=O or-OH.Described monose is selected from more than one in glucose, fructose, galactolipin, ribose, glycogen and deoxyribose.
Described material with carbon element is selected from more than one in the derived carbon of activated carbon, Graphene, expanded graphite, CNT, mesoporous carbon, carbon fiber, hollow carbon balls and carbide.
As preferably, it is hydrothermal carbonization method by method compound with material with carbon element carbonization to monose or polysaccharide.
The present invention additionally provides the positive electrode including above-mentioned additive, it is made up of conductive agent, electroactive substance and additive, described conductive agent is material with carbon element, specially natural carbon material or synthesis material with carbon element, and conductive agent mass percent in positive electrode is 30～70wt%；Natural carbon material is: activated carbon, acetylene black, SuperP, carbon black；Synthesis material with carbon element is: SWCN, multi-walled carbon nano-tubes, carbon fiber, expanded graphite, Graphene, amorphous graphite or ordered mesopore carbon/poromerics, and ordered mesopore carbon/poromerics includes: the material with carbon element that ordered mesopore carbon, microporous carbon ball, graphene oxide, oxidation activity carbon, oxidation acetylene black, polyaniline heating carbonization are formed.
Described electroactive substance is sulphur, and sulphur mass percent in positive electrode is 30～70wt%；Described additive is shitosan or phosphonized chitosan, and additive mass percent in positive electrode is 0.01～5wt%.
The conductive carbon material used in the present invention has good adsorption capacity and has high-specific surface area, big pore volume, loose structure, in the positive pole sulfur-bearing active material used in the present invention sulfur content number and the existence form of sulphur determine the specific discharge capacity of unit mass electrode material.The positive electrode additive used in the present invention is the carbohydrate containing strong lone pair electrons group, including but not limited to the product that the polysaccharide of the monose such as glucose, fructose, galactolipin, ribose, deoxyribose and polymerization thereof is compound with material with carbon element.The many lithium sulfides produced in discharge process can form interaction in modes such as coordinations with additive, make its dissolving in the electrolytic solution be suppressed, the cathode of lithium burn into capacity attenuation that the loss that therefore can effectively reduce active material and " effect of shuttling back and forth " that caused by the dissolving of many lithium sulfides are caused rapidly wait affect.
Present invention also offers the preparation method of above-mentioned positive electrode, method is: be supported in material with carbon element by additive, then uses ball-milling method, melted inhalation or chemical synthesis to be mixed with sulphur by the material with carbon element being loaded with additive；Or it is: use ball-milling method, melted inhalation or chemical synthesis to prepare mixing material after being mixed with sulphur by material with carbon element, then additive is supported in mixing material.Ball-milling method is simple, can be beaten by solid particle little to nano-grade size, be capable of more uniform mixing simultaneously, after conductive carbon material, positive electrode active materials sulphur and additive are ground uniformly, and rotating speed ball milling that i.e. can be certain.Melted inhalation makes sulphur enter in the hole of conductive carbon material with the form of liquid or steam at a certain temperature, on the one hand can increase sulfur content in positive electrode, on the other hand can suppress the loss of polysulfide to a certain extent.Chemistry method of formation is by sodium thiosulfate and acid reaction, generates sulfur granules uniformly, have an advantage in that enabling to sulphur is more evenly distributed in the suspension of conductive carbon material, and the sulfur granules of generation is little.The method in material with carbon element or mixing material that is supported on by additive is for using the physical admixture such as grinding or ball milling.
Present invention also offers a kind of positive plate being coated with above-mentioned positive electrode, adopt and prepare with the following method: positive electrode and binding agent are mixed according to the mass ratio of 9:1 and is scattered in dispersant, anode sizing agent is prepared after magnetic agitation 12h, anode sizing agent is coated on aluminium foil and makes sheet, after drying, roll-in, prepare positive plate.Described binding agent is the one in Kynoar, polyoxyethylene and cyclodextrin, and dispersant is 1-METHYLPYRROLIDONE or ultra-pure water.
Prepared positive plate is assembled lithium-sulfur cell together with negative pole and barrier film.Negative pole be lithium metal, barrier film be Celgard2400 type barrier film, electrolyte mainly selects some linear ethers and carbonate-based solvent, supports that solute can be selected for bis trifluoromethyl sulfonic acid Asia acid amides lithium, lithium hexafluoro phosphate etc..Battery pattern can manufacture any size and the battery of the present invention of configuration with any appropriate ways well known by persons skilled in the art.The design configuration of these battery pack includes but not limited to flat, prismatic, cylindrical, stacking shape etc..Having of battery is necessarily affected by the size of battery case.The battery pattern used in the present invention is cylindrical.
Accompanying drawing explanation
Fig. 1 is the discharge curve of the C/S composite ball-milling method in comparative example.
Fig. 2 is the discharge curve of the positive electrode ball-milling method prepared in the embodiment of the present invention 2.
Fig. 3 is the comparison diagram of the C/S/Glucose composite in embodiment 1 and the C/S composite discharge cycles in comparative example.
Fig. 4 is the discharge cycles comparison diagram of the C/S/Glucose composite of the different glucose contents in embodiment 1,2,3.
Fig. 5 is the discharge cycles comparison diagram of C/S/Glucose composite under the different discharge-rates in embodiment 4,5.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention done detailed specific description, but protection scope of the present invention is not limited to following example.
The additive provided in present invention product after to be material with carbon element compound with monose or the polysaccharide carbonization that is polymerized by monose, containing strong lone pair electrons group in described monose and polysaccharide.Described strong lone pair electrons group is-C=O ,-OH etc..
Described monose is selected from more than one in glucose, fructose, galactolipin, ribose and deoxyribose.Described material with carbon element is selected from more than one in the derived carbon of activated carbon, Graphene, expanded graphite, CNT, mesoporous carbon, carbon fiber, hollow carbon balls and carbide.
Below hydrothermal carbonization method is illustrated: glucide chooses the glucose containing strong lone pair electrons group, material with carbon element chooses Super P, take a certain amount of glucose to be scattered in 80ml deionized water with Super P, ultrasonic disperse 10min in ultrasonic cleaning instrument, transfer in 100mL hydrothermal reaction kettle, 160 DEG C of reaction 48h.After question response terminates, suction filtration, 65 DEG C are dried, and grind, i.e. obtain the composite of glucose and Super P, be the additive of follow-up interpolation.
Comparative example
Selection specific surface area is 1000cm2·g-1, pore volume is 2.3cm3·g-1Activated carbon (AR, Tianjin Ke Miou) be conductive material carbon (C): 2.8g, positive electrode active materials sulphur (S): 1.2g, prepare C/S composite by ball-milling method.The rotating speed of ball milling is: (300 ,-200) rpm, ball milling 2h (ball milling 10min, stop 10min).
C/S composite (C:60wt%, S:40wt%) mix and be dispersed in preparation in 1-METHYLPYRROLIDONE or ultra-pure water obtain anode sizing agent with binding agent (Kynoar of 10%) 9:1 in mass ratio, after magnetic agitation 12h, slurry is coated on aluminium foil, 7h drying, roll-in, section is dried in baking oven, i.e. obtaining required anode pole piece, the thickness of anode pole piece is 100 μm.Negative pole is the lithium paper tinsel that thickness is about 100 μm, and the barrier film of employing is Celegard2400 polypropylene screen, and electrolyte is 1mol L-1Bis trifluoromethyl sulfonic acid Asia acid amides lithium (LiN (CF3SO2)2)/dimethoxy-ethane (DME)+1,3-dioxolanes (DOL) (volume ratio 1:1).Said modules being assembled in prismatic battery with the structure of positive pole/dividing plate/negative pole, whole cell assembling processes all completes in glove box.To carry out constant current charge-discharge test under the current density of 0.1C, battery testing temperature is typically near room temperature 25 DEG C.Test result shows that this battery first discharge specific capacity is: 946mAh g-1, after 50 circulations, specific discharge capacity is: 213mAh g-1, result is as shown in Figure 1.
Embodiment 1
Additive provided in the present embodiment is the composite of glucose (Glucose) and Super P, preparation method is as follows: takes 1g Super P and is scattered in 80ml deionized water with 5g glucose, ultrasonic disperse 10min in ultrasonic cleaning instrument, transfer in 100mL hydrothermal reaction kettle, 160 DEG C of reaction 48h.After question response terminates, suction filtration, 65 DEG C are dried, and grind, obtain the composite of glucose and Super P, i.e. additive, then additive is joined in C/S system, complex method is identical with comparative example, i.e. prepare C/S/Glucose composite positive pole, C:58wt% in positive electrode, S:40.00wt%, additive: 2.00wt%.Prepared by anode pole piece, the method for assembled battery and battery testing is all identical with comparative example.Battery charging and discharging test result shows, the first charge-discharge specific capacity of battery is: 1097mAh g-1.After 50 circulations, specific capacity is: 835mAh g-1, after 100 circulations, specific capacity is: 803mAh g-1.By compared with the battery being not added with additive, adding battery discharge specific capacity after glucose and Super P composite additives, cyclical stability is greatly improved.
Embodiment 2
Additive provided in the present embodiment is the composite of 2.5g glucose (Glucose) and 1g Super P, and preparation method is same as in Example 1.Being joined by prepared additive in C/S system, complex method is identical with comparative example, i.e. prepares C/S/Glucose composite positive pole, C:58wt% in positive electrode, S:40.00wt%, additive: 2.00wt%.Prepared by anode pole piece, the method for assembled battery and battery testing is all identical with comparative example.Battery constant current charging-discharging test display, first discharge specific capacity is: 1106mAh g-1.After 50 circulations, specific capacity is: 843mAh g-1, after 100 circulations, specific capacity is 821mAh g-1.Result is as shown in Figure 2.By compared with the battery being not added with additive, after adding glucose and Super P composite additives, battery discharge specific capacity and cyclical stability are greatly improved, and battery performance is greatly improved.
Embodiment 3
Additive provided in the present embodiment is the composite of 1g glucose (Glucose) and 1g Super P, and preparation method is same as in Example 1.Being joined by prepared additive in C/S system, complex method is identical with comparative example, i.e. prepares C/S/Glucose composite positive pole, C:58wt% in positive electrode, S:40.00wt%, additive: 2.00wt%.Prepared by anode pole piece, the method for assembled battery and battery testing is all identical with comparative example.Battery constant current charging-discharging test display, first discharge specific capacity is: 1123mAh g-1.After 50 circulations, specific capacity is: 849mAh g-1, after 100 circulations, specific capacity is: 815mAh g-1.By compared with the battery being not added with additive, after adding glucose and Super P composite additives, battery discharge specific capacity and cyclical stability are greatly improved, and battery performance is greatly improved.
Embodiment 4
With glucose (Glucose) and Super P composite as the additive of positive electrode in the present embodiment, taking additive quality is: 20mg.Preparation method is same as in Example 1.Being joined by prepared additive in C/S system, complex method is identical with comparative example, i.e. prepares C/S/Glucose composite positive pole, C:38wt% in positive electrode, S:60.00wt%, additive: 2.00wt%.Prepared by anode pole piece, the method for assembled battery and battery testing is all identical with comparative example.To carry out constant current charge-discharge test under the current density of 0.1C, battery testing temperature is typically near room temperature 25 DEG C.Test result shows this battery, and first discharge specific capacity is: 1078mAh g-1, after 50 circulations, specific discharge capacity is: 814mAh g-1, after 100 circulations, specific discharge capacity is: 792mAh g-1。
Embodiment 5
With glucose (Glucose) and Super P composite as the additive of positive electrode in the present embodiment, taking additive quality is: 20mg.Preparation method is same as in Example 1.Being joined by prepared additive in C/S system, complex method is identical with comparative example, i.e. prepares C/S/Glucose composite positive pole, C:58wt% in positive electrode, S:40.00wt%, additive: 2.00wt%.Prepared by anode pole piece, the method for assembled battery and battery testing is all identical with comparative example.To carry out constant current charge-discharge test under the current density of 0.5C, battery testing temperature is typically near room temperature 25 DEG C.Test result shows this battery, and first discharge specific capacity is: 683mAh g-1, after 50 circulations, discharge capacity is: 590mAh g-1, after 100 circulations, discharge capacity is: 513mAh/g.This result is it can be shown that discharge under 0.5C multiplying power, and battery special capacity fade is little, and cycle performance of battery is preferable.
Embodiment 6
With fructose (Fructose) and the Super P composite additive as positive electrode in the present embodiment.Take 1g Super P to be scattered in 80ml deionized water with 2.5g fructose, ultrasonic disperse 10min in ultrasonic cleaning instrument, transfer in 100mL hydrothermal reaction kettle, 160 DEG C of reaction 48h.After question response terminates, suction filtration, 65 DEG C are dried, and grind, obtain the composite of fructose and Super P.Use ball-milling method to be combined with C/S system, obtain C/S/Fructose composite positive pole.C:58wt% in positive electrode, S:41.50wt%, additive: 0.50wt%.Prepared by anode pole piece, the method for assembled battery and battery testing is all identical with comparative example.Test result shows this battery, and first discharge specific capacity is: 1135mAh g-1, after 50 circulations, specific discharge capacity is: 858mAh g-1, after 100 circulations, specific discharge capacity is: 832mAh g-1。
Embodiment 7
With ribose (Ribose) and the Super P composite additive as positive electrode in the present embodiment.Take 1g Super P to be scattered in 80ml deionized water with 2.5g ribose, ultrasonic disperse 10min in ultrasonic cleaning instrument, transfer in 100mL hydrothermal reaction kettle, 160 DEG C of reaction 48h.After question response terminates, suction filtration, 65 DEG C are dried, and grind, obtain the composite of ribose and Super P.Use ball-milling method to be combined with C/S system, obtain C/S/Ribose composite positive pole.C:58wt% in positive electrode, S:40.00wt%, additive: 2.00wt%.Prepared by anode pole piece, the method for assembled battery and battery testing is all identical with comparative example.Test result shows this battery, and first discharge specific capacity is: 1113 mAh g-1, after 50 circulations, specific discharge capacity is: 835mAh g-1, after 100 circulations, specific discharge capacity is: 807mAh g-1。
Embodiment 8
With galactan (Galactan) and the Super P composite additive as positive electrode in the present embodiment.Take 1gSuper P to be scattered in 80ml deionized water with 2.5g galactan, ultrasonic disperse 10min in ultrasonic cleaning instrument, transfer in 100mL hydrothermal reaction kettle, 160 DEG C of reaction 48h.After question response terminates, suction filtration, 65 DEG C are dried, and grind, obtain the composite of galactan and Super P.Use ball-milling method to be combined with C/S system, obtain C/S/Galactan composite positive pole.C:58wt% in positive electrode, S:38.00wt%, additive: 4.00wt%.Prepared by anode pole piece, the method for assembled battery and battery testing is all identical with comparative example.Test result shows that this battery first discharge specific capacity is: 1090mAh g-1, after 50 circulations, specific discharge capacity is: 807mAh g-1, after 100 circulations, specific discharge capacity is: 783mAh g-1。
Embodiment 9
With glycogen (Glycogen) and the Super P composite additive as positive electrode in the present embodiment.Take 1g SuperP to be scattered in 80ml deionized water with 2.5g glycogen, ultrasonic disperse 10min in ultrasonic cleaning instrument, transfer in 100mL hydrothermal reaction kettle, 160 DEG C of reaction 48h.After question response terminates, suction filtration, 65 DEG C are dried, and grind, obtain the composite of glycogen and Super P.Use ball-milling method to be combined with C/S system, obtain C/S/Glycogen composite positive pole.C:58wt% in positive electrode, S:40.00wt%, additive: 2.00wt%.Prepared by anode pole piece, the method for assembled battery and battery testing is all identical with comparative example.Test result shows that this battery first discharge specific capacity is: 1079mAh g-1, and after 50 circulations, specific discharge capacity is: 817mAh g-1, and after 100 circulations, specific discharge capacity is: 780mAh g-1.
Battery charging and discharging test result obtained by various embodiments above and comparative example shows in Table 1.
Table 1
As seen from Table 1, with the addition of each embodiment of adsorbent in positive electrode, compared with comparative example, the discharge capacity first of battery increases, and cycle performance is significantly improved.
The C/S/Glucose composite provided in embodiments of the invention 1 is with the comparison diagram of C/S composite discharge cycles in comparative example as shown in Figure 3.
In embodiments of the invention 1, embodiment 2, the discharge cycles comparison diagram of the C/S/Glucose composite of the different glucose contents provided in embodiment 3 is as shown in Figure 4.
Under the different discharge-rates provided in embodiments of the invention 4 and embodiment 5, the discharge cycles comparison diagram of C/S/Glucose composite is as shown in Figure 5.
Proposed by the invention by introduce in carbon sulphur positive electrode the polysaccharide related on a small quantity containing the monose such as the glucose containing strong lone pair electrons group such as substantial amounts of-C=O ,-OH, fructose, galactolipin, ribose, deoxyribose and polymerization thereof compound with material with carbon element after as additive, suppress to discharge the dissolving of the many lithium sulfides of intermediate product by absorption, and the cathode of lithium burn into capacity attenuation that the loss that can effectively reduce active material and the many lithium sulfides " effect of shuttling back and forth " that cause dissolved thereof are caused waits rapidly to be affected.Utilize the C/S/A composite that heretofore described preparation method is obtained as lithium-sulphur cell positive electrode, serviceability and the cycle life of this lithium-sulfur cell system can be effectively improved.
Claims (7)
1. the additive being applied in lithium-sulfur cell, it is characterised in that: described additive product after to be material with carbon element compound with monose or the polysaccharide carbonization that is polymerized by monose, containing strong lone pair electrons group in described monose and polysaccharide；Described strong lone pair electrons group is-C=O or-OH；Described monose is selected from more than one in glucose, fructose, galactolipin, ribose, glycogen and deoxyribose；The method that described carbonization is combined is hydrothermal carbonization method, particularly as follows: take a certain amount of material with carbon element and monose or polysaccharide is scattered in 80mL deionized water, ultrasonic disperse 10 min in ultrasonic cleaning instrument, transferring in 100 mL hydrothermal reaction kettles, 160 DEG C of reaction 48 h, after question response terminates, suction filtration, 65 DEG C are dried, and grind, and i.e. obtain material with carbon element and monose or the composite of polysaccharide.
Additive the most according to claim 1, it is characterised in that: described material with carbon element is selected from more than one in the derived carbon of activated carbon, Graphene, expanded graphite, CNT, mesoporous carbon, carbon fiber, hollow carbon balls and carbide.
3. the lithium sulfur battery anode material being added with additive described in claim 1, it is characterized in that being made up of conductive agent, electroactive substance and additive, described conductive agent is natural carbon material or synthesis material with carbon element, and conductive agent mass percent in positive electrode is 30 ~ 70
wt% ；Described electroactive substance is sulphur, and sulphur mass percent in positive electrode is 30 ~ 70 wt%；Described additive is the product after material with carbon element is combined with monose or polysaccharide carbonization, and additive mass percent in positive electrode is 0.01 ~ 5
wt%。
4. the preparation method of the positive electrode described in claim 3, it is characterised in that preparation method is: be supported in material with carbon element by additive, then uses ball-milling method, melted inhalation or chemical synthesis to be mixed with sulphur by the material with carbon element being loaded with additive；Or it is: use ball-milling method, melted inhalation or chemical synthesis to prepare mixing material after being mixed with sulphur by material with carbon element, then additive is supported in mixing material.
5.
The preparation method of positive electrode according to claim 4, it is characterised in that: the method being supported on by additive in material with carbon element or mixing material is to use to grind or the physical admixture of ball milling.
6. the positive plate of the positive electrode being coated with described in claim 3, it is characterized in that adopting preparing with the following method: positive electrode and binding agent are mixed and are dispersed according to the mass ratio of 9:1 in dispersant, prepare anode sizing agent, anode sizing agent is coated on aluminium foil and makes sheet, after drying, roll-in, prepare positive plate.
Positive plate the most according to claim 6, it is characterised in that: described binding agent is the one in Kynoar, polyoxyethylene and cyclodextrin, and dispersant is 1-METHYLPYRROLIDONE or ultra-pure water.
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| CN104900880B (en) * | 2015-06-03 | 2017-07-11 | 中国地质大学（武汉） | A kind of lithium-sulfur battery composite anode material and preparation method thereof |
| CN106058150A (en) * | 2016-08-15 | 2016-10-26 | 柔电（武汉）科技有限公司 | Electrode of lithium sulfur battery and preparation method thereof |
| CN109560279B (en) * | 2018-11-30 | 2021-08-10 | 陕西科技大学 | Method for preparing porous biological carbon lithium-sulfur battery positive electrode material from ceiba |
| CN109546132B (en) * | 2018-11-30 | 2021-05-14 | 陕西科技大学 | Preparation method of dandelion/sugar biochar composite structure |
| CN109546148B (en) * | 2018-11-30 | 2021-07-06 | 陕西科技大学 | Method for preparing porous irregular spherical biological carbon lithium sulfur battery positive electrode material from chestnut peels |
| CN109360975B (en) * | 2018-11-30 | 2021-03-19 | 陕西科技大学 | Preparation method of composite biological carbon structure loaded sulfur |
| CN109244467B (en) * | 2018-11-30 | 2021-04-30 | 陕西科技大学 | Method for preparing biochar negative electrode material from setaria viridis |
| CN109592661B (en) * | 2018-11-30 | 2020-06-30 | 陕西科技大学 | Method for preparing biochar from corn stigma |
| CN109574005B (en) * | 2018-11-30 | 2020-06-02 | 陕西科技大学 | Preparation method of lithium-sulfur battery negative electrode biological carbon material |
| CN109592662B (en) * | 2018-11-30 | 2020-09-22 | 陕西科技大学 | Preparation method of biochar negative electrode material for lithium-sulfur battery |
| CN114230836B (en) * | 2021-12-18 | 2023-10-20 | 河北金力新能源科技股份有限公司 | Modified lithium-sulfur battery diaphragm and preparation method thereof |
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| US6210831B1 (en) * | 1997-12-19 | 2001-04-03 | Moltech Corporation | Cathodes comprising electroactive sulfur materials and secondary batteries using same |
| JP2013528913A (en) * | 2010-06-17 | 2013-07-11 | リンダ， フェイ ナザール， | Multi-component electrode for rechargeable batteries |
| CN102569730A (en) * | 2012-01-31 | 2012-07-11 | 中南大学 | Preparation method for positive plate of lithium-sulfur battery |
| CN102780001B (en) * | 2012-07-27 | 2014-09-17 | 中南大学 | Lithium-sulfur battery cathode material and preparation method thereof |
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