CN103515614A - Additive for battery, cathode material containing same and preparation method for cathode material - Google Patents
Additive for battery, cathode material containing same and preparation method for cathode material Download PDFInfo
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- CN103515614A CN103515614A CN201310464652.6A CN201310464652A CN103515614A CN 103515614 A CN103515614 A CN 103515614A CN 201310464652 A CN201310464652 A CN 201310464652A CN 103515614 A CN103515614 A CN 103515614A
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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 an additive for a lithium sulphur battery, a cathode material containing the same and a preparation method for the cathode material. The additive is a product formed by carbonizing and compounding a carbon material and monosaccharide or polysaccharide polymerized by monosaccharide, wherein the monosaccharide and the polysaccharide contain intensive arc pair electron groups. The intensive arc pair electron group is -C=O or -OH. The monosaccharide is selected from glucose, fructose, galactose, ribose, glycogen and ribodesose. The conductive carbon material in the cathode material has good adsorption capacity, large specific surface area, and high pore volume and adopts a porous structure, and the electrochemical active substance is sulphur. The additive is the substance containing the intensive arc pair electron group. Polysulfide lithium produced during the discharge process can perform interaction with the additive in a mode of coordination and the like, so that the dissolution of the polysulfide lithium in electrolyte is restrained, and the loss of the active substance and the lithium cathode corrosion, rapid capacity fading influence and the like can be effectively reduced.
Description
Technical field
The present invention relates to a kind of novel carbon-sulfur positive electrode that is applied to lithium-sulfur cell and preparation method thereof, relate in particular to the additive of carbon sulphur positive electrode, the preparation method of the monose such as the glucose that specifically relates to contain strong lone pair electrons group, fructose, galactolipin, ribose, deoxyribose and the polysaccharide of polymerization thereof and the additive A of the compound rear generation of material with carbon element and corresponding C/S/A positive electrode, and lithium-sulfur cell preparation, assembling and measuring technology based on this C/S/A positive electrode.
Background technology
Current, with Li
2coO
2, LiFePO
4deng having obtained very widely application for the lithium rechargeable battery of positive electrode.But, being limited to the theoretical specific energy of these positive electrodes, existing lithium-ion battery system is difficult to meet the fields such as following mobile 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, wherein especially take elemental sulfur as anodal, the lithium metal lithium-sulfur rechargeable battery system that is negative pole is as outstanding, about the research and development of this system, have become study hotspot nearly ten years.
Single sulphur positive electrode is by electrochemical reaction S
8+ 16Li → 8Li
2s counts its specific capacity up to 1675mAhg
-1, be that in known solid positive electrode, energy density is the highest, and sulphur simple substance reserves are abundant, cheap, safety and low toxicity, thereby there is very wide application prospect.But sulphur simple substance is typical electronic body (5 * 10
-30scm
-1, 25 ℃), electro-chemical activity is poor; Electric discharge end product Li
2s compares volumetric expansion with electric discharge initial condition and reaches 87%, causes sulphur positive pole loosely organized and even destroyed in charge and discharge cycles; The lithium polysulfide Li that sulfur electrode forms at certain level of charge
2s
n(n=6～8) are soluble in electrolyte, and diffuse to lithium electrode and react with its generation self discharge and generate lithium polysulfide Li
2s
n(n=3～4), cause lithium corrosion.While Li
2s
n(n=3～4) are spread back again sulfur electrode and are oxidized to Li
2s
nafter (n=6～8), diffuse to again lithium electrode surface, occur " effect of shuttling back and forth ".The effect of shuttling back and forth that the dissolving of polysulfide causes is one of difficult problem of lithium-sulfur cell most critical, has significantly reduced utilance, specific capacity and the cycle performance of sulphur, has increased 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 conductive
2s and Li
2s
2can cover with the form of solid film the surface of positive electrode active materials, thereby hinder the electrochemical reaction between electrolyte and electrode active material.
In order to address the above problem, people have proposed many solutions.Mainly to set about from improving the aspects such as material with carbon element, binding agent, polymer overmold, cathode of lithium modification, positive electrode additive.
For positive electrode, Chinese patent CN102208645A discloses the coated sulphur of a kind of amorphous carbon, Chinese patent CN101986443A discloses the coated sulphur of a kind of nano hollow carbon pipe, 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 is loose to be adsorbed in the tube-surface and pipe of described conductive polymer nanometer pipe, forms the filamentary structure of hollow.Chinese patent CN102074704A discloses a kind of preparation method of secondary lithium-sulfur battery anode adhesive.For negative material, Chinese patent CN1508893 discloses a kind of negative pole of lithium-sulfur cell, and described negative pole comprises the protective layer of lithium metal, one deck pretreatment layer and one deck 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 be mainly adopt that material with carbon element is coated, polymer overmold or the coated sulphur of nano material additive etc. improve lithium-sulfur cell cycle performance.
Summary of the invention
The invention provides a kind of new additive agent, utilize the specific function group on a small amount of additive of introducing to adsorb polysulfide, effectively to suppress the dissolving of polysulfide in charge and discharge process, reduce the adverse effect that the effect of shuttling back and forth is brought, improve lithium-sulfur cell cycle performance.
The technical scheme that realizes above-mentioned purpose is:
Be applied to the additive in lithium-sulfur cell, described additive be material with carbon element and monose or compound by the polysaccharide carbonization of monose polymerization after product, in described monose and polysaccharide, contain strong lone pair electron group.Described strong lone pair electron 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, carbon nano-tube, mesoporous carbon, carbon fiber, hollow carbon balls and carbide.
As preferably, by monose or polysaccharide and the compound method of material with carbon element carbonization, be hydrothermal carbonization method.
The positive electrode that includes above-mentioned additive is also provided in the present invention, by conductive agent, electroactive substance and additive, formed, described conductive agent is material with carbon element, is specially natural carbon material or synthetic material with carbon element, and the mass percent of conductive agent in positive electrode is 30～70wt%; Natural carbon material is: activated carbon, acetylene black, SuperP, carbon black; Synthetic material with carbon element is: Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, carbon fiber, expanded graphite, Graphene, amorphous graphite or ordered mesopore carbon/poromerics, ordered mesopore carbon/poromerics comprises: the material with carbon element that ordered mesopore carbon, microporous carbon ball, graphene oxide, oxidation activity carbon, oxidation acetylene black, polyaniline heating carbonization form.
Described electroactive substance is sulphur, and the mass percent of sulphur in positive electrode is 30～70wt%; Described additive is shitosan or phosphonized chitosan, and the mass percent of additive in positive electrode is 0.01～5wt%.
The conductive carbon material using in the present invention has good adsorption capacity and has high-specific surface area, large pore volume, loose structure, and in the anodal sulfur-bearing active material using in the present invention, the number of sulfur content and the existence form of sulphur have determined the specific discharge capacity of unit mass electrode material.The positive electrode additive using in the present invention is the carbohydrate that contains strong lone pair electrons group, including but not limited to the polysaccharide of the monose such as glucose, fructose, galactolipin, ribose, deoxyribose and polymerization thereof and the compound product of material with carbon element.The many lithium sulfides that produce in discharge process can form and interact with the modes such as coordination and additive, therefore make its dissolving in electrolyte suppressed, can effectively reduce the loss of active material and the impact such as rapidly of the cathode of lithium burn into capacity attenuation that caused by " effect of shuttling back and forth " that the dissolving of many lithium sulfides causes.
The present invention also provides the preparation method of above-mentioned positive electrode, and method is: additive is loaded in material with carbon element, then adopt ball-milling method, melting inhalation or chemical synthesis load to be had the material with carbon element of additive mix with sulphur; Or be: after adopting ball-milling method, melting inhalation or chemical synthesis that material with carbon element is mixed with sulphur, make composite material, then additive is loaded in composite material.Ball-milling method is simple, solid particle can be beaten littlely of nano-grade size, and can realize more simultaneously and mixing, after conductive carbon material, positive electrode active materials sulphur and additive are ground evenly, rotating speed ball milling that can be certain.Melting inhalation makes sulphur enter in the hole of conductive carbon material with the form of liquid state or steam at a certain temperature, can increase sulfur content in positive electrode on the one hand, can suppress to a certain extent on the other hand the loss of polysulfide.Chemistry method of formation is by sodium thiosulfate and acid reaction, generates uniformly sulfur granules in the suspension of conductive carbon material, and its advantage is to make sulphur to be more evenly distributed, and the sulfur granules of generation is little etc.The method that additive is loaded in material with carbon element or composite material is the physical admixture such as employing grinding or ball milling.
The present invention also provides a kind of positive plate that is coated with above-mentioned positive electrode, adopt preparation with the following method: positive electrode and binding agent are mixed according to the mass ratio of 9:1 and be scattered in dispersant, after magnetic agitation 12h, make anode sizing agent, anode sizing agent is coated on aluminium foil and makes sheet, after oven dry, roll-in, make positive plate.Described binding agent is a kind of in Kynoar, polyoxyethylene and cyclodextrin, and dispersant is 1-METHYLPYRROLIDONE or ultra-pure water.
Prepared positive plate is assembled together with barrier film to lithium-sulfur cell with negative pole.Negative pole is that lithium metal, barrier film are Celgard2400 type barrier film, and electrolyte is mainly selected some linear ethers and carbonates solvent, supports solute can select the sub-acid amides lithium of bis trifluoromethyl sulfonic acid, lithium hexafluoro phosphate etc.Battery pattern can any appropriate ways well known by persons skilled in the art be manufactured the battery of the present invention of any size and configuration.That the design configuration of these battery pack includes but not limited to is flat, prismatic, cylindrical, stacking shape etc.The have certain influence of the size of battery case to battery.The battery pattern adopting in the present invention is cylindrical.
Accompanying drawing explanation
Fig. 1 is the discharge curve that the C/S composite material in comparative example is used ball-milling method.
Fig. 2 is the discharge curve of ball-milling method for the positive electrode that makes in the embodiment of the present invention 2.
Fig. 3 is C/S/Glucose composite material in embodiment 1 and the comparison diagram of the C/S composite material discharge cycles in comparative example.
Fig. 4 is the discharge cycles comparison diagram of the C/S/Glucose composite material of the different glucose contents in embodiment 1,2,3.
Fig. 5 is the discharge cycles comparison diagram of C/S/Glucose composite material under the different discharge-rates in embodiment 4,5.
Embodiment
Below in conjunction with specific embodiment, the present invention is done to detailed specific description, but protection scope of the present invention is not limited to following examples.
The additive providing in the present invention be material with carbon element and monose or by the polysaccharide carbonization of monose polymerization compound after product, in described monose and polysaccharide, contain strong lone pair electron group.Described strong lone pair electron 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, carbon nano-tube, mesoporous carbon, carbon fiber, hollow carbon balls and carbide.
Below hydrothermal carbonization method is illustrated: glucide is chosen the glucose that contains strong lone pair electron group, material with carbon element is chosen Super P, getting a certain amount of glucose and Super P is scattered in 80ml deionized water, ultrasonic dispersion 10min in ultrasonic cleaning instrument, transfer in 100mL hydrothermal reaction kettle 160 ℃ of reaction 48h.After question response finishes, suction filtration, 65 ℃ are dry, grind, and obtain the composite material of glucose and Super P, are the additive of follow-up interpolation.
Comparative example
Selecting specific area is 1000cm
2g
-1, pore volume is 2.3cm
3g
-1active carbon (AR， Tianjin Ke Miou) be electric conducting material carbon (C): 2.8g, positive electrode active materials sulphur (S): 1.2g, prepares C/S composite material by ball-milling method.The rotating speed of ball milling is: (300 ,-200) rpm, ball milling 2h (ball milling 10min, stops 10min).
C/S composite material (C:60wt%, S:40wt%) and binding agent (10% Kynoar) in mass ratio 9:1 mix and be dispersed in 1-METHYLPYRROLIDONE or ultra-pure water preparation and obtain anode sizing agent, after magnetic agitation 12h, slurry is coated on aluminium foil, in baking oven, dry 7h oven dry, roll-in, section, obtain required anode pole piece, the thickness of anode pole piece is 100 μ m.Negative pole is the lithium paper tinsel that thickness is about 100 μ m, and the barrier film of employing is Celegard2400 polypropylene screen, and electrolyte is 1molL
-1the sub-acid amides lithium of bis trifluoromethyl sulfonic acid (LiN (CF
3sO
2)
2)/dimethoxy-ethane (DME)+DOX (DOL) (volume ratio 1:1).Structure by said modules with positive pole/dividing plate/negative pole is assembled in prismatic battery, and whole battery pack process of assembling all completes in glove box.To carry out constant current charge-discharge test under the current density of 0.1C, battery testing temperature is generally near 25 ℃ of room temperatures.Test result shows that this battery first discharge specific capacity is: 946mAhg
-1, after 50 circulations, specific discharge capacity is: 213mAhg
-1, the results are shown in Figure shown in 1.
The additive providing in the present embodiment is the composite material of glucose (Glucose) and Super P, preparation method is as follows: get 1g Super P and 5g glucose and be scattered in 80ml deionized water, ultrasonic dispersion 10min in ultrasonic cleaning instrument, transfer in 100mL hydrothermal reaction kettle 160 ℃ of reaction 48h.After question response finishes, suction filtration, 65 ℃ are dry, grind, obtain the composite material of glucose and Super P, be additive, then additive is joined in C/S system, complex method is identical with comparative example, make C/S/Glucose composite positive pole, C:58wt% in positive electrode, S:40.00wt%, additive: 2.00wt%.The method of anode pole piece preparation, 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: 1097mAhg
-1.After 50 circulations, specific capacity is: 835mAhg
-1, after 100 circulations, specific capacity is: 803mAhg
-1.By not comparing with adding additivated battery, battery discharge specific capacity after interpolation glucose and Super P composite additives, cyclical stability improves greatly.
The additive providing in the present embodiment is the composite material of 2.5g glucose (Glucose) and 1g Super P, and preparation method is identical with embodiment 1.Prepared additive is joined in C/S system, and complex method is identical with comparative example, makes C/S/Glucose composite positive pole, C:58wt% in positive electrode, S:40.00wt%, additive: 2.00wt%.The method of anode pole piece preparation, assembled battery and battery testing is all identical with comparative example.Battery constant current charging-discharging test demonstration, first discharge specific capacity is: 1106mAhg
-1.After 50 circulations, specific capacity is: 843mAhg
-1, after 100 circulations, specific capacity is 821mAhg
-1.The results are shown in Figure shown in 2.By not comparing with adding additivated battery, after interpolation glucose and Super P composite additives, battery discharge specific capacity and cyclical stability improve greatly, and battery performance is greatly improved.
The additive providing in the present embodiment is the composite material of 1g glucose (Glucose) and 1g Super P, and preparation method is identical with embodiment 1.Prepared additive is joined in C/S system, and complex method is identical with comparative example, makes C/S/Glucose composite positive pole, C:58wt% in positive electrode, S:40.00wt%, additive: 2.00wt%.The method of anode pole piece preparation, assembled battery and battery testing is all identical with comparative example.Battery constant current charging-discharging test demonstration, first discharge specific capacity is: 1123mAhg
-1.After 50 circulations, specific capacity is: 849mAhg
-1, after 100 circulations, specific capacity is: 815mAhg
-1.By not comparing with adding additivated battery, after interpolation glucose and Super P composite additives, battery discharge specific capacity and cyclical stability improve greatly, and battery performance is greatly improved.
In the present embodiment with glucose (Glucose) and Super P composite material the additive as positive electrode, get additive quality and be: 20mg.Preparation method is identical with embodiment 1.Prepared additive is joined in C/S system, and complex method is identical with comparative example, makes C/S/Glucose composite positive pole, C:38wt% in positive electrode, S:60.00wt%, additive: 2.00wt%.The method of anode pole piece preparation, 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 generally near 25 ℃ of room temperatures.Test result shows this battery, and first discharge specific capacity is: 1078mAhg
-1, after 50 circulations, specific discharge capacity is: 814mAhg
-1, after 100 circulations, specific discharge capacity is: 792mAhg
-1.
In the present embodiment with glucose (Glucose) and Super P composite material the additive as positive electrode, get additive quality and be: 20mg.Preparation method is identical with embodiment 1.Prepared additive is joined in C/S system, and complex method is identical with comparative example, makes C/S/Glucose composite positive pole, C:58wt% in positive electrode, S:40.00wt%, additive: 2.00wt%.The method of anode pole piece preparation, 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 generally near 25 ℃ of room temperatures.Test result shows this battery, and first discharge specific capacity is: 683mAhg
-1, after 50 circulations, discharge capacity is: 590mAhg
-1, after 100 circulations, discharge capacity is: 513mAh/g.This result can show, under 0.5C multiplying power, discharges, and battery special capacity fade is little, and cycle performance of battery is better.
In the present embodiment, take the additive that fructose (Fructose) and Super P composite material be positive electrode.Get 1g Super P and 2.5g fructose and be scattered in 80ml deionized water, in ultrasonic cleaning instrument, ultrasonic dispersion 10min, transfers in 100mL hydrothermal reaction kettle, 160 ℃ of reaction 48h.After question response finishes, suction filtration, 65 ℃ are dry, grind, and obtain the composite material of fructose and Super P.Adopt ball-milling method and C/S system compound, obtain C/S/Fructose composite positive pole.C:58wt% in positive electrode, S:41.50wt%, additive: 0.50wt%., the method for anode pole piece preparation, assembled battery and battery testing is all identical with comparative example.Test result shows this battery, and first discharge specific capacity is: 1135mAhg
-1, after 50 circulations, specific discharge capacity is: 858mAhg
-1, after 100 circulations, specific discharge capacity is: 832mAhg
-1.
Embodiment 7
In the present embodiment, take the additive that ribose (Ribose) and Super P composite material be positive electrode.Get 1g Super P and 2.5g ribose and be scattered in 80ml deionized water, in ultrasonic cleaning instrument, ultrasonic dispersion 10min, transfers in 100mL hydrothermal reaction kettle, 160 ℃ of reaction 48h.After question response finishes, suction filtration, 65 ℃ are dry, grind, and obtain the composite material of ribose and Super P.Adopt ball-milling method and C/S system compound, obtain C/S/Ribose composite positive pole.C:58wt% in positive electrode, S:40.00wt%, additive: 2.00wt%., the method for anode pole piece preparation, assembled battery and battery testing is all identical with comparative example.Test result shows this battery, and first discharge specific capacity is: 1113mAhg
-1, after 50 circulations, specific discharge capacity is: 835mAhg
-1, after 100 circulations, specific discharge capacity is: 807mAhg
-1.
Embodiment 8
In the present embodiment, take the additive that galactan (Galactan) and Super P composite material be positive electrode.Get 1g Super P and 2.5g galactan and be scattered in 80ml deionized water, in ultrasonic cleaning instrument, ultrasonic dispersion 10min, transfers in 100mL hydrothermal reaction kettle, 160 ℃ of reaction 48h.After question response finishes, suction filtration, 65 ℃ are dry, grind, and obtain the composite material of galactan and Super P.Adopt ball-milling method and C/S system compound, obtain C/S/Galactan composite positive pole.C:58wt% in positive electrode, S:38.00wt%, additive: 4.00wt%., the method for anode pole piece preparation, assembled battery and battery testing is all identical with comparative example.Test result shows that this battery first discharge specific capacity is: 1090mAhg
-1, after 50 circulations, specific discharge capacity is: 807mAhg
-1, after 100 circulations, specific discharge capacity is: 783mAhg
-1.
Embodiment 9
In the present embodiment, take the additive that glycogen (Glycogen) and Super P composite material be positive electrode.Get 1g Super P and 2.5g glycogen and be scattered in 80ml deionized water, in ultrasonic cleaning instrument, ultrasonic dispersion 10min, transfers in 100mL hydrothermal reaction kettle, 160 ℃ of reaction 48h.After question response finishes, suction filtration, 65 ℃ are dry, grind, and obtain the composite material of glycogen and Super P.Adopt ball-milling method and C/S system compound, obtain C/S/Glycogen composite positive pole.C:58wt% in positive electrode, S:40.00wt%, additive: 2.00wt%., the method for anode pole piece preparation, assembled battery and battery testing is all identical with comparative example.Test result shows that this battery first discharge specific capacity is: 1079mAhg-1, after 50 circulations, specific discharge capacity is: 817mAhg-1, after 100 circulations, specific discharge capacity is: 780mAhg-1.
The resulting battery charging and discharging test result of each embodiment and comparative example is presented in table 1 above.
Table 1
As seen from Table 1, added each embodiment of adsorbent in positive electrode, compared with comparative example, the discharge capacity first of battery increases, and cycle performance is significantly improved.
In the C/S/Glucose composite material providing in embodiments of the invention 1 and comparative example, the comparison diagram of C/S composite material discharge cycles as shown in Figure 3.
In embodiments of the invention 1, embodiment 2, and the discharge cycles comparison diagram of the C/S/Glucose composite material of the different glucose contents that provide in embodiment 3 as shown in Figure 4.
Under the different discharge-rates that provide in embodiments of the invention 4 and embodiment 5, the discharge cycles comparison diagram of C/S/Glucose composite material as shown in Figure 5.
Proposed by the invention pass through to introduce that to relate on a small quantity polysaccharide and the material with carbon element of the monose such as the glucose that contains a large amount of-C=O ,-OH etc. and contain strong lone pair electrons group, fructose, galactolipin, ribose, deoxyribose and polymerization thereof compound rear as additive in carbon sulphur positive electrode, by absorption suppress the to discharge dissolving of the many lithium sulfides of intermediate product, can effectively reduce the impact such as rapidly of cathode of lithium burn into capacity attenuation that " effect of shuttling back and forth " that the loss of active material and many lithium sulfides of dissolving thereof cause cause.Utilize C/S/A composite material that the preparation method described in the present invention obtains as lithium-sulphur cell positive electrode, can effectively improve serviceability and the cycle life of this lithium-sulfur cell system.
Claims (10)
1. be applied to the additive in lithium-sulfur cell, it is characterized in that: described additive be material with carbon element and monose or compound by the polysaccharide carbonization of monose polymerization after product, in described monose and polysaccharide, contain strong lone pair electron group.
2. additive according to claim 1, is characterized in that: described strong lone pair electron group for-C=O or-OH.
3. additive according to claim 1, is characterized in that: described monose is selected from more than one in glucose, fructose, galactolipin, ribose, glycogen and deoxyribose.
4. additive according to claim 1, is characterized in that: described material with carbon element is selected from more than one in the derived carbon of activated carbon, Graphene, expanded graphite, carbon nano-tube, mesoporous carbon, carbon fiber, hollow carbon balls and carbide.
5. additive according to claim 1, is characterized in that: by monose or polysaccharide and the compound method of material with carbon element carbonization, be hydrothermal carbonization method.
6. a lithium sulfur battery anode material that is added with additive described in claim 1, it is characterized in that being formed by conductive agent, electroactive substance and additive, described conductive agent is material with carbon element, be specially natural carbon material or synthetic material with carbon element, the mass percent of conductive agent in positive electrode is 30～70wt%; Described electroactive substance is sulphur, and the mass percent of sulphur in positive electrode is 30～70wt%; Described additive is material with carbon element and monose or the polysaccharide carbonization product after compound, and the mass percent of additive in positive electrode is 0.01～5wt%.
7. the preparation method of positive electrode claimed in claim 6, is characterized in that preparation method is: additive is loaded in material with carbon element, then adopt ball-milling method, melting inhalation or chemical synthesis load to be had the material with carbon element of additive mix with sulphur; Or be: after adopting ball-milling method, melting inhalation or chemical synthesis that material with carbon element is mixed with sulphur, make composite material, then additive is loaded in composite material.
8. the preparation method of positive electrode according to claim 7, is characterized in that: additive is loaded on to the physical admixture that the method in material with carbon element or composite material is employing grinding or ball milling.
9. a positive plate that is coated with positive electrode claimed in claim 6, it is characterized in that adopting preparation with the following method: positive electrode and binding agent are mixed and be dispersed in dispersant according to the mass ratio of 9:1, make anode sizing agent, anode sizing agent is coated on aluminium foil and makes sheet, after oven dry, roll-in, make positive plate.
10. positive plate according to claim 9, is characterized in that: described binding agent is a kind of in Kynoar, polyoxyethylene and cyclodextrin, and dispersant is 1-METHYLPYRROLIDONE or ultra-pure water.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104900880A (en) * | 2015-06-03 | 2015-09-09 | 中国地质大学（武汉） | Lithium-sulfur battery composite positive electrode 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 |
| CN109244467A (en) * | 2018-11-30 | 2019-01-18 | 陕西科技大学 | A kind of method that herba setariae viridis grass prepares biological carbon negative pole material |
| CN109360975A (en) * | 2018-11-30 | 2019-02-19 | 陕西科技大学 | A kind of compound bio carbon structure load sulphur preparing process |
| CN109546148A (en) * | 2018-11-30 | 2019-03-29 | 陕西科技大学 | A kind of method that chestnut peel prepares porous irregular spherical biological carbon lithium-sulfur cell negative electrode material |
| CN109546132A (en) * | 2018-11-30 | 2019-03-29 | 陕西科技大学 | A kind of preparation method of dandelion/sugar biological carbon composite construction |
| CN109560279A (en) * | 2018-11-30 | 2019-04-02 | 陕西科技大学 | A kind of method that kapok prepares multiporous biological carbon lithium-sulfur cell negative electrode material |
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| CN109592662A (en) * | 2018-11-30 | 2019-04-09 | 陕西科技大学 | A kind of preparation method of the biological carbon negative pole material of lithium-sulfur cell |
| CN114230836A (en) * | 2021-12-18 | 2022-03-25 | 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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| CN104900880A (en) * | 2015-06-03 | 2015-09-09 | 中国地质大学（武汉） | Lithium-sulfur battery composite positive electrode material and preparation method thereof |
| WO2016192389A1 (en) * | 2015-06-03 | 2016-12-08 | 中国地质大学（武汉） | Lithium sulfur battery composite positive electrode 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 |
| CN109592662A (en) * | 2018-11-30 | 2019-04-09 | 陕西科技大学 | A kind of preparation method of the biological carbon negative pole material of lithium-sulfur cell |
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| 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 |
| CN109360975A (en) * | 2018-11-30 | 2019-02-19 | 陕西科技大学 | A kind of compound bio carbon structure load sulphur preparing process |
| 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 |
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| 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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