CN103500848A - Battery additive, positive material containing additive and preparation method of positive material - Google Patents

Battery additive, positive material containing additive and preparation method of positive material Download PDF

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CN103500848A
CN103500848A CN201310464485.5A CN201310464485A CN103500848A CN 103500848 A CN103500848 A CN 103500848A CN 201310464485 A CN201310464485 A CN 201310464485A CN 103500848 A CN103500848 A CN 103500848A
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additive
positive electrode
lithium
preparation
hydrotalcite
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CN103500848B (en
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周成冈
李琦旸
张珊
黄子沛
吴金平
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China University of Geosciences
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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
    • H01M4/624—Electric conductive fillers
    • 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

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a lithium sulfur battery additive, a positive material containing the additive and a preparation method of the positive material. The additive is hydrotalcite, a hydrotalcite-like compound or layered metal hydroxide which is loaded in a carbon oxide material and contains rich and exposed intensive arc pair electronic groups -OH. A conductive carbon material of the positive material disclosed by the invention is high in adsorption capacity, high in specific surface area and high in pore volume and has a porous structure; an electrochemical active substance of the positive material is sulfur. The additive is a substance containing the intensive arc pair electronic groups. Polysulfide lithium generated in a discharging process can interact with the additive in a mode of coordination and the like, so that dissolving of the polysulfide lithium in electrolyte can be suppressed; therefore, the loss of active substances can be effectively reduced, and the problems of corrosion and quick capacity attenuation of a lithium negative electrode are solved.

Description

Additives for battery, contain positive electrode of this additive and preparation method thereof
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, specifically relate to containing of carbonoxide material load hydrotalcite abundant and exposure-strong lone pair electrons group of OH, the preparation method of the additive such as houghite and layered metal hydroxides 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 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 the electric discharge initial condition and reaches 87%, causes the 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 the lithium corrosion.While Li 2s n(n=3～4) are spread back again sulfur electrode and are oxidized to Li 2s ndiffuse to again lithium electrode surface after (n=6～8), 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 a kind of amorphous carbon and has coated sulphur, Chinese patent CN101986443A discloses a kind of nano hollow carbon pipe and has coated 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 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 is mainly to adopt material with carbon element coating, polymer overmold or nano material additive coating sulphur etc. to improve the 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 the reduction adverse effect that effect brings of shuttling back and forth, improve the lithium-sulfur cell cycle performance.
The technical scheme that realizes above-mentioned purpose is:
A kind of additive be applied in lithium-sulfur cell, described additive, for using hydrotalcite, houghite or the layered metal hydroxides of carbonoxide material load, includes divalent metal and trivalent metal cation in described hydrotalcite, houghite and layered metal hydroxides; Interlayer includes inorganic anion, complex anion or biochemistry anion.
Described divalent metal is Mg 2+, Zn 2+, Ca 2+, Fe 2+, Ni 2+, Mn 2+, Co 2+and Cu 2+in a kind of, described trivalent metal cation is Al 3+, Cr 3+, Fe 3+, Sc 3+, Co 3+, Ga 3+, Mn 3+and Ln 3+in a kind of, Fe wherein 2+, Ni 2+, Mn 2+, Co 2+, Cu 2+, Fe 3+, Co 3+and Mn 3+there is electro-chemical activity.Described hydrotalcite, houghite and layered metal hydroxides are for peeling off fully or partly peeling off.
The positive electrode that includes above-mentioned additive also is 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%; The 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 hydrotalcite, houghite or the layered metal hydroxides that contains strong lone pair electrons group-OH, and the mass percent of additive in positive electrode is 0.83～3.33wt%.
The conductive carbon material used 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 used in the present invention, the existence form of the number of sulfur content and sulphur has determined the specific discharge capacity of unit mass electrode material.The positive electrode additive used in the present invention is that described additive is hydrotalcite, houghite or the layered metal hydroxides that contains the strong lone pair electrons group-OH that enriches and expose.The many lithium sulfides that produce in discharge process can be with mode and additive formation interactions such as coordinations, therefore make its dissolving in electrolyte suppressed, can effectively reduce the loss of active material and 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 waits rapidly impact.
The present invention also provides the preparation method of above-mentioned positive electrode, and method is: additive is loaded in the carbonoxide material, then adopt ball-milling method, melting inhalation or chemical synthesis load to be had the material with carbon element of additive mix with sulphur.Ball-milling method is simple, solid particle can be beaten littlely of nano-grade size, simultaneously can realize more evenly mixing, and after grinding evenly by conductive carbon material, positive electrode active materials sulphur and additive, rotating speed ball milling that can be certain.The 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.The 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 the material with carbon element after oxidation is coprecipitation method or roasting-restoring method or hydrothermal synthesis method or ion-exchange.The method for oxidation of described material with carbon element is Hummers method or improvement Hummers method, strong acid (as the concentrated sulfuric acid, red fuming nitric acid (RFNA)) and on a small quantity strong oxidizer (as KMnO 4, HClO 4, O 3) acting in conjunction under realize oxidation in various degree.
The present invention also provides a kind of positive plate that is coated with above-mentioned positive electrode, adopt the preparation of following method: the mass ratio by positive electrode and binding agent according to 9:1 mixes and is scattered in dispersant, make anode sizing agent after magnetic agitation 12h, 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 inferior acid amides lithium of bis trifluoromethyl sulfonic acid, lithium hexafluoro phosphate etc.The 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 adopted in the present invention is cylindrical.
The accompanying drawing explanation
Fig. 1 is the discharge curve that the C/S composite material in Comparative Examples is used ball-milling method.
Fig. 2 is the positive electrode that makes in the embodiment of the present invention 2 discharge curve with ball-milling method.
Fig. 3 is C/S/CMA composite material in embodiment 1 and the comparison diagram of the C/S composite material discharge cycles in Comparative Examples.
The discharge cycles comparison diagram of the C/S/CMA composite material that Fig. 4 is the different CMA content in embodiment 1,2,3.
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.
Additive described in the present invention, for using hydrotalcite, houghite or the layered metal hydroxides of carbonoxide material load, includes divalent metal and trivalent metal cation in described hydrotalcite, houghite and layered metal hydroxides; Interlayer includes inorganic anion, complex anion or biochemistry anion.
Described divalent metal is Mg 2+, Zn 2+, Ca 2+, Fe 2+, Ni 2+, Mn 2+, Co 2+and Cu 2+in a kind of, described trivalent metal cation is Al 3+, Cr 3+, Fe 3+, Sc 3+, Co 3+, Ga 3+, Mn 3+and Ln 3+in a kind of, Fe wherein 2+, Ni 2+, Mn 2+, Co 2+, Cu 2+, Fe 3+, Co 3+and Mn 3+there is electro-chemical activity.Described hydrotalcite, houghite and layered metal hydroxides are for peeling off fully or partly peeling off.
Comparative Examples
Selecting specific area is 1800cm 2g -1, pore volume is 1.2cm 3g -1active carbon (AR, Nanjing Xian Feng nanometer) be electric conducting material carbon (C): 2.8g, positive electrode active materials sulphur (S): 1.2g, prepare the C/S composite material 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 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, dry 7h oven dry, roll-in, section in baking oven, 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 the Celegard2400 polypropylene screen, and electrolyte is 1molL -1the inferior 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 the constant current charge-discharge test under the current density of 0.1C, the 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.
Embodiment 1
In the present embodiment, material with carbon element is selected active carbon, and the method for oxidation of active carbon is the Hummers method, is specially: after active carbon is carried out to ball milling with ball mill with (300rpm ,-200rpm), use K 2s 2o 4concentrated sulfuric acid solution and P 2o 5, react 6h under 80 ℃, after the standing and suction filtration of room temperature by product 60 ℃ of dryings, obtain the active carbon of pre-oxidation.The active carbon of pre-oxidation is slowly added in a certain amount of concentrated sulfuric acid, and gradation adds potassium permanganate, after-10 ℃ of reaction 1.5h, be warming up to 35 ℃ of reaction 1.5h; After adding again a certain amount of distilled water to react 1h under 40 ℃, be warming up to 80 ℃ of reaction 1h; Stop reaction adding again 30% the hydrogen peroxide of 20ml in solution after.Product is standing centrifugal and repeatedly dry after washing through supercooling, obtain the magnesium oxide/absorbent charcoal sample.
In the present embodiment, additive is selected magnalium hydrotalcite, and the method that magnalium hydrotalcite is loaded in the material with carbon element after oxidation is as follows: measure respectively a certain amount of 30% hydrogen peroxide and distilled water to flask, and add successively 0.0306gMg (NO 3) 26H 2o, 0.113g Al (NO 3) 39H 2o, 0.594g urea, 0.2g OAC, after ultrasonic being uniformly dispersed, at 150 ℃ of lower condensation heating back flow reaction 8h.Reaction is cooled to room temperature after finishing, suction filtration, and with deionized water washing 2-3 time, dry under room temperature, obtain magnesium oxide/absorbent charcoal load magnalium hydrotalcite sample.
In the present embodiment, additive is the aforesaid magnalium hydrotalcite through the magnesium oxide/absorbent charcoal load, in the present embodiment, the addition of additive is higher, specifically get 1.7g activated carbon (C), 0.1g magnesium oxide/absorbent charcoal load magnalium hydrotalcite (CMA), 1.2g elemental sulfur (S) prepares positive electrode, the preparation method is identical with Comparative Examples.C:56.67wt% in the C/S/CMA composite positive pole finally made, S:40.00wt%, CMA:3.33wt%, the method for anode pole piece preparation, assembled battery and battery testing is all with identical in Comparative Examples.Battery is shown through the charge-discharge test result, and the first charge-discharge specific capacity of battery is: 1163.66mAhg -1.After 50 circulations, specific capacity is: 857.03mAhg -1, after 100 circulations, specific capacity is: 571.7mAhg -1.Compare by the battery with not adding additive, add the rear battery first discharge specific capacity of magnesium oxide/absorbent charcoal load magnalium hydrotalcite (CMA) and increase, and cyclical stability improves greatly.
Embodiment 2
In the present embodiment, additive is the aforesaid magnalium hydrotalcite through the magnesium oxide/absorbent charcoal load, and in the present embodiment, the addition of additive is medium, and the preparation method is identical with Comparative Examples.C:58.33wt% in the C/S/CMA composite positive pole finally made, S:40.00wt%, CMA:1.67wt%, the method for anode pole piece preparation, assembled battery and battery testing is all with identical in Comparative Examples.By battery, through constant current charge-discharge, test shows, first discharge specific capacity is: 1470.73mAhg -1.After 50 circulations, specific capacity is: 1130.03mAhg -1, after 100 circulations, specific capacity is 813mAhg -1.The results are shown in Figure shown in 2.Compare by the battery with not adding additive, add the rear battery discharge specific capacity of magnesium oxide/absorbent charcoal load magnalium hydrotalcite (CMA) and cyclical stability and greatly improve, and battery performance is greatly improved.
Embodiment 3
In the present embodiment, additive is the aforesaid magnalium hydrotalcite through the magnesium oxide/absorbent charcoal load, and in the present embodiment, the addition of additive is lower, and the preparation method is identical with Comparative Examples.C:39.17wt% in the C/S/CMA composite positive pole finally made, S:60.00wt%, CMA:0.83wt%, the method for anode pole piece preparation, assembled battery and battery testing is all with identical in Comparative Examples.By battery, through constant current charge-discharge, test shows, first discharge specific capacity is: 1286.58mAhg -1.After 50 circulations, specific capacity is: 1014.03mAhg -1, after 100 circulations, specific capacity is: 760.4mAhg -1.Compare by the battery with not adding additive, add the rear battery discharge specific capacity of magnesium oxide/absorbent charcoal load magnalium hydrotalcite (CMA) and cyclical stability and greatly improve, and battery performance is greatly improved.
Embodiment 4
The houghite that in the present embodiment, additive is the magnesium oxide/absorbent charcoal load (Ni-Al hydrotalcite, CMN), its preparation method is identical with embodiment 1, C:58.33wt% in the C/S/CMN composite positive pole finally made, S:40.00wt%, CMA:1.67wt%, the method for anode pole piece preparation, assembled battery and battery testing is all with identical in Comparative Examples.Test result shows that this battery first discharge specific capacity is: 1506mAhg -1, after 50 circulations, specific discharge capacity is: 1201mAhg -1, after 100 circulations, specific discharge capacity is: 962mAhg -1.
The resulting battery charging and discharging test result of above each embodiment and Comparative Examples is presented in table 1
Table 1
Figure BDA0000391840910000061
As seen from Table 1, added each embodiment of adsorbent in positive electrode, compared with Comparative Examples, the discharge capacity first of battery increases, and cycle performance is significantly improved.
In the C/S/CMA composite material provided in embodiments of the invention 1 and Comparative Examples, 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/CMA composite material of the different hydrotalcite content that provide in embodiment 3 as shown in Figure 4.
Proposed by the invention passing through introduced the magnesium oxide/absorbent charcoal hydrotalcite of loaded type that contain on a small quantity-OH etc. contains strong lone pair electrons group and metal ion in carbon sulphur positive electrode, houghite and hydroxide etc. are as third party's additive, by the dissolving of the many lithium sulfides of intermediate product that adsorb to suppress to discharge, can effectively reduce the cathode of lithium burn into capacity attenuation that " effect of shuttling back and forth " that many lithium sulfides of the loss of active material and dissolving thereof cause cause and wait rapidly impact.The C/S/A composite material that utilizes the preparation method described in the present invention to obtain, as lithium-sulphur cell positive electrode, can effectively improve serviceability and the cycle life of this lithium-sulfur cell system.

Claims (9)

1. the additive be applied in lithium-sulfur cell, it is characterized in that: described additive, for using hydrotalcite, houghite or the layered metal hydroxides of carbonoxide material load, includes divalent metal and trivalent metal cation in described hydrotalcite, houghite and layered metal hydroxides; Interlayer includes inorganic anion, complex anion or biochemistry anion.
2. additive according to claim 1, it is characterized in that: described divalent metal is Mg 2+, Zn 2+, Ca 2+, Fe 2+, Ni 2+, Mn 2+, Co 2+and Cu 2+in a kind of, described trivalent metal cation is Al 3+, Cr 3+, Fe 3+, Sc 3+, Co 3+, Ga 3+, Mn 3+and Ln 3+in a kind of, Fe wherein 2+, Ni 2+, Mn 2+, Co 2+, Cu 2+, Fe 3+, Co 3+and Mn 3+there is electro-chemical activity.
3. additive according to claim 1 is characterized in that: described hydrotalcite, houghite and layered metal hydroxides are for peeling off fully or part is peeled off.
4. a lithium sulfur battery anode material that is added with the described additive of 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 hydrotalcite, houghite or layered metal hydroxides, and the mass percent of additive in positive electrode is 0.83～3.33wt%.
5. the preparation method of positive electrode claimed in claim 4 is characterized in that the preparation method is: additive is loaded in the material with carbon element after oxidation, then adopt ball-milling method, melting inhalation or chemical synthesis load to be had the material with carbon element of additive mix with sulphur.
6. the preparation method of positive electrode according to claim 5 is characterized in that: the method that additive is loaded in the material with carbon element after oxidation is coprecipitation method or roasting-restoring method or hydrothermal synthesis method or ion-exchange.
7. the preparation method of positive electrode according to claim 5 is characterized in that: the method for oxidation of described material with carbon element is Hummers method or improvement Hummers method.
8. a positive plate that is coated with positive electrode claimed in claim 4, it is characterized in that adopting following method preparation: mix and be dispersed in dispersant by positive electrode and binding agent 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.
9. positive plate according to claim 8 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
WO2016107564A1 (en) * 2014-12-29 2016-07-07 中国地质大学（武汉） Composite positive material for lithium-sulphur battery with high rate performance and preparation method
CN106876712A (en) * 2015-12-14 2017-06-20 中国科学院大连化学物理研究所 A kind of method of polysulfide ion shuttle in suppression lithium-sulfur cell
CN109103427A (en) * 2018-08-01 2018-12-28 北京师范大学 A kind of composite material, preparation method and its application for lithium-sulphur cell positive electrode

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CN102185127A (en) * 2011-04-07 2011-09-14 武汉理工大学 Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery
CN102956875A (en) * 2012-10-31 2013-03-06 中南大学 Carbon-coated zinc-base hydrotalcite preparation and application method of carbon-coated zinc-base hydrotalcite in zinc-nickel secondary battery
CN103201885A (en) * 2010-06-17 2013-07-10 L·F·纳扎尔 Multicomponent electrodes for rechargeable batteries

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CN103201885A (en) * 2010-06-17 2013-07-10 L·F·纳扎尔 Multicomponent electrodes for rechargeable batteries
CN102185127A (en) * 2011-04-07 2011-09-14 武汉理工大学 Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery
CN102956875A (en) * 2012-10-31 2013-03-06 中南大学 Carbon-coated zinc-base hydrotalcite preparation and application method of carbon-coated zinc-base hydrotalcite in zinc-nickel secondary battery

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016107564A1 (en) * 2014-12-29 2016-07-07 中国地质大学（武汉） Composite positive material for lithium-sulphur battery with high rate performance and preparation method
CN106876712A (en) * 2015-12-14 2017-06-20 中国科学院大连化学物理研究所 A kind of method of polysulfide ion shuttle in suppression lithium-sulfur cell
CN109103427A (en) * 2018-08-01 2018-12-28 北京师范大学 A kind of composite material, preparation method and its application for lithium-sulphur cell positive electrode
CN109103427B (en) * 2018-08-01 2020-10-16 北京师范大学 Composite material for lithium-sulfur battery positive electrode, preparation method and application thereof

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