CN101562261A - Lithium-sulfur battery and preparation method thereof - Google Patents

Lithium-sulfur battery and preparation method thereof Download PDF

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CN101562261A
CN101562261A CNA2009100851370A CN200910085137A CN101562261A CN 101562261 A CN101562261 A CN 101562261A CN A2009100851370 A CNA2009100851370 A CN A2009100851370A CN 200910085137 A CN200910085137 A CN 200910085137A CN 101562261 A CN101562261 A CN 101562261A
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lithium
sulfur
carbon
compound
electrode
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吴锋
吴生先
陈人杰
陈实
苏岳峰
李丽
王国庆
陈君政
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Beijing Institute of Technology BIT
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a lithium-sulfur battery and a preparation method thereof, which belongs to the field of electrochemical batteries. The lithium-sulfur battery uses a carbon material as a negative electrode and elemental sulfur as a positive electrode, and introduces non-lithium third electrode to perform lithium-embedding treatment on the negative electrode so as to prevent the safety problem caused by directly adopting the metal lithium as the negative electrode. The main component of the non-lithium third electrode is a lithium-rich compound with certain irreversible lithium-removing property; and in the preparation process of an elemental sulfur positive electrode material, the third electrode lithium-rich compound is mixed into the material according to a mass percent of between 10 and 40 percent; and when the material is prepared into an electrode, the electrode and the carbon negative electrode form the lithium-sulfur battery. In the charging process of the battery for the first time, the lithium-rich compound achieves the lithium-embedding operation to the negative electrode.

Description

A kind of lithium-sulfur cell and preparation method thereof
Technical field
The present invention relates to a kind of lithium-sulfur cell and preparation method thereof, particularly extremely replace lithium anode, thereby solve the safety issue of lithium-sulfur cell, belong to field of electrochemical batteries by introducing the 3rd.
Background technology
In recent years, along with the continuous progress of science and technology, the fast development of various electronic products requires used chemical power source to have characteristics such as light weight, volume is little, capacity is big.Though, improve the exploitation that the energy density of battery must be leaned on new material and new system by a relatively large margin by improving the performance that existing battery material preparation and cell making process can improve battery to a certain extent.
In the battery system of numerous researchs, the metal lithium-sulfur cell is considered to tool application potential.Elemental sulfur theoretical specific capacity as positive active material is 1675mAh/g, and specific energy is that 2600Wh/kg (generates Li after lithium metal and the sulphur complete reaction 2S), be higher than existing lithium rechargeable battery material LiCoO far away 2, LiMnO 2And LiFePO 4Deng.Simultaneously the elemental sulfur positive electrode has the source and enriches low price, advantage such as environmentally friendly.Yet also there are a lot of problems in the development of lithium-sulfur cell.
Lithium-sulfur cell adopts lithium metal as negative pole, in the charge and discharge cycles process, the dissolving repeatedly and the deposition reaction of lithium metal will take place in negative terminal surface, efflorescence take place and form dendrite on the lithium metal surface, fail safe to battery constitutes a serious threat, and has also shortened the cycle life of battery simultaneously.
In order to improve the cycle performance of lithium metal; solve its safety issue; people have carried out the trial of a lot of aspects, and concrete measure comprises that the material that adds with the lithium metal reaction forms lithium alloy, forms protective layer, with protective agent electrode surface is applied with chemical method in lithium electrode surface.
K.Naio etc. utilize the helical form ethylene oxide chain nuclear in the polyvinyl alcohol dimethyl ether to play the principle of lithium ion channeling at charging and interdischarge interval, can charge and discharge cycle in by the polyvinyl alcohol absorption of dimethyl ether is formed uniform protection layer to the lithium metallic surface.M.Ishikawa etc. are by adding silver iodide (AlI in organic electrolyte 3) or magnesium iodide (MgI 2) form the growth that alloy suppresses Li dendrite.But in these examples, skin covering of the surface can not keep uniform state after the cycle that discharges and recharges that repeats and one section soak time.Efficiency for charge-discharge can not obtain gratifying raising.
There is patent to propose in electrolyte solution, to add LiAlCl 43SO 2, and make solution form the method for protective layer in lithium electrode surface with containing that the lithium metallic surface reacts.Also have and propose to be coated with the protective layer that contains lithium metasilicate or lithium borate in lithium electrode surface by vacuum evaporating.But after circulation many times, because the insertion of lithium ion and deviating from, protective layer becomes unstable and breaks, thereby makes a large amount of electrolyte solutions by slit on the protective layer and lithium Metal Contact, causes the decomposition of electrolyte solution and the lasting decline of capacity.
Summary of the invention
The object of the present invention is to provide lithium-sulfur cell of a kind of new construction composition and preparation method thereof, by adopting rich lithium compound as the 3rd utmost point, directly add in the positive pole of lithium-sulfur cell, utilize the 3rd utmost point that the technology in lithium source is provided, but in battery, do not increase by the 3rd utmost point, only need realize that the embedding lithium of anticathode is handled by initial charge to battery, thus cyclicity and the safety issue of having avoided direct employing metal lithium electrode to be brought.
Content of the present invention comprises: the lithium-sulfur cell that this new construction is formed is to be negative pole with the material with carbon element, is positive pole with elemental sulfur, elemental sulfur compound or sulfur-based compound, introduces nonmetal lithium the 3rd utmost point anticathode and carries out pre-embedding lithium processing.Nonmetal lithium the 3rd utmost point main component is to have the reversible scarcely rich lithium compound that takes off lithium character, in the preparation process of elemental sulfur positive electrode, the 3rd is rich in lithium compound mixes with 10 ~ 40% mass percent, makes behind the electrode to constitute lithium-sulfur cell with the carbon negative pole together.Battery rich lithium compound in the initial charge process is realized the embedding lithium behavior of anticathode.Accept the lithium-sulfur cell that carbon negative pole behind the embedding lithium and the anodal composition of sulphur can charge and discharge.Carry out the irreversible lithium in small amounts compound that takes off behind the lithium, will stay in the middle of the positive pole, can improve the electric conductivity and the pore structure of sulphur positive pole as additive.
The elemental sulfur that the present invention relates to is sublimed sulfur or high purity sulphur; The elemental sulfur compound comprises: sulphur/carbon material compound (material with carbon element is carbon nano-tube, carbon nano-fiber, active carbon, carbon aerogels, carbon black etc.), sulphur/conductive polymer composite (conducting polymer is polyaniline, polypyrrole, polythiophene etc.), sulphur/inorganic oxide compound (inorganic oxide is yittrium oxide, lanthana, cerium oxide, titanium oxide etc.); Sulfur-based compound comprises: Li 2S n(n 〉=1), organosulfur compound, carbon sulphur polymer ((C 2S x) n, x=2.5 ~ 10, n 〉=2).
The material with carbon element that the present invention relates to comprises: graphite, petroleum coke, MCMB, middle phase charcoal fiber, high polymer pyrolytic carbon, carbon nano-tube etc.
The reversible scarcely lithium compound that takes off lithium character that has that the present invention relates to comprises: LiMO 2(M=Co, Ni, Mn, Cu, Cr, Fe etc.), LiMn 2-xM xO 4(when M=Ni, Co, Cu, 0＜x＜1; When M=Cr, Fe, V, 0＜x＜0.5), LiNi xM 1-xO 2(M=Co, Mn, Cu, Cr, Fe, V, La, Al, Mg, Ga, Zn etc., 0＜x＜1), LiNi xMn yCo zO 2(x+y+z=1), LiFePO 4, Li 2FeO 4, Li 3-xM xN (M=Co, Ni, Cu, Cr, V etc., 0＜x＜1), Li 7-xMn xN 4(0＜x＜1), Li 3-xFe xN 2(0＜x＜1), Li 2S, Li 2S 2Deng.
The lithium-sulfur cell that the present invention is prepared, electrolytical range of choice can be the electrolyte systems of organic liquid, ionic liquid, solid-state, gel state.Organic liquid electrolyte can be selected for use and contain glycol dimethyl ether (DME), 1, a kind of organic solvent of 3-dioxolane (DOL), oxolane (THF), diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ortho-xylene etc. or the mixture of several organic solvents.Electrolyte lithium salt can be lithium hexafluoro phosphate (LiPF 6), LiBF4 (LiBF 4), hexafluoroarsenate lithium (LiAsF 6), lithium perchlorate (LiClO 4), trifluoromethyl sulfonic acid lithium (LiCF 3SO 3), bis trifluoromethyl sulfimide lithium (LiN (CF 3SO 2) 2).Solid electrolyte can be Li 2O-B 2O 3-Li 2SO 4, Li 2S-SiS 2-P 2S 5, Li 2S-SiS 2-Li 3PO 4, LiI-Li 2S-SiS 2, Li 3.6Si 0.6P 0.4O 4, Li 3.3PO 3.9N 0.17Gel electrolyte is made up of two parts: as macromolecular scaffold, another part is above-mentioned organic liquid electrolyte to a part by PVDF-HFP (Kynoar-hexafluoropropylene copolymer), PAN (polyacrylonitrile), PMMA (polymethyl methacrylate), PVC (polyvinyl chloride) or the mixture between them.
Beneficial effect
The lithium-sulfur cell that new construction proposed by the invention is formed, mode with the 3rd utmost point replaces direct use metal lithium electrode, compare with other manufacture method of lithium-sulfur cell, this invent prepared cycle performance of battery and security performance be improved significantly, and this method technology is simple, safe and reliable, and control accurately, with low cost, thereby have a good application prospect.
Description of drawings
Fig. 1 is the lithium-sulfur cell electrode schematic diagram of the inventive method
Fig. 2 is for adopting lithium-sulfur cell sulfur electrode charging and discharging curve figure of the present invention
Fig. 3 is for adopting lithium-sulfur cell sulfur electrode cycle performance figure of the present invention
Embodiment
Embodiment 1
Is anodal with the sublimed sulfur, mixes mass percent and be 10% LiNi 0.5Co 0.5O 2Mixture and acetylene black, Kynoar (PVDF) mix by mass ratio at 80: 10: 10, with N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent, in stainless steel jar mill with the speed ball milling 4h of 200rpm, the paste slurries that obtain are uniformly coated on the collector Al paper tinsel, then in 60 ℃ vacuum drying chamber the oven dry 20 hours standby.With graphite is negative material, mix at 85: 10: 5 by mass ratio with acetylene black, Kynoar (PVDF), with N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent, in stainless steel jar mill with the speed ball milling 2h of 200rpm, the paste slurries that obtain are uniformly coated on the collector Cu paper tinsel, then in 60 ℃ vacuum drying chamber the oven dry 20 hours standby.With the sulfur electrode is anodal, graphite electrode is a negative pole, Celgrad2300 is a barrier film, 1mol/L bis trifluoromethyl sulfonic acid imide li (LiTFSI)/glycol dimethyl ether (DME)+1, and 3-dioxolane (DOL) (volume ratio 1: 1) is assembled into lithium-sulfur cell for electrolyte.
Battery at first carries out constant current charge with the current density of 50mA/g, and the charging upper voltage limit is 4.6V, and this process is that graphite cathode carries out the processing of embedding lithium.Carry out constant-current discharge with the current density of 50mA/g then, the discharge lower voltage limit is 1.0V.Battery carries out charge and discharge cycles with the current density of 50mA/g subsequently, and voltage range is 1.0V ~ 3.0V.The first discharge specific capacity of sulfur electrode is 857.4mAh/g, has occurred 2 tangible discharge platforms on the discharge curve.20 times circulation back specific discharge capacity also remains on 613.7mAh/g, has demonstrated good cyclical stability.
Embodiment 2
Is anodal with the carbyne polysulfide, mixes mass percent and be 40% LiNi 0.5Co 0.5O 2Mixture and acetylene black, polyethylene glycol oxide (PEO) mix by mass ratio at 80: 10: 10, with the deionized water is solvent, in stainless steel jar mill with the speed ball milling 4h of 200rpm, the paste slurries that obtain are uniformly coated on the collector Al paper tinsel, then in 60 ℃ vacuum drying chamber the oven dry 20 hours standby.With carbonaceous mesophase spherules (MCMB) is negative material, mix at 85: 10: 5 by mass ratio with acetylene black, Kynoar (PVDF), with N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent, in stainless steel jar mill with the speed ball milling 2h of 200rpm, the paste slurries that obtain are uniformly coated on the collector Cu paper tinsel, then in 60 ℃ vacuum drying chamber the oven dry 20 hours standby.With the carbyne polysulfide electrode is positive pole, and the MCMB electrode is a negative pole, and Celgrad2300 is a barrier film, and 1M PP14-TFSI il electrolyte is that electrolyte is assembled into lithium-sulfur cell.
Battery at first carries out constant current charge with the current density of 50mA/g, and the charging upper voltage limit is 4.6V, and this process is handled for the MCMB negative pole carries out the embedding lithium.Carry out constant-current discharge with the current density of 50mA/g then, the discharge lower voltage limit is 1.0V.Battery carries out charge and discharge cycles with the current density of 50mA/g subsequently, and voltage range is 1.0V ~ 3.0V.The first discharge specific capacity of carbyne polysulfide electrode is 769.2mAh/g, and a very long discharge platform is arranged near 2.1V.Also leave the specific discharge capacity of 413.6mAh/g after 20 circulations.
Embodiment 3
Is anodal with the sublimed sulfur, mixes mass percent and be 10% Li 2.6Co 0.4N, mixture and acetylene black, Kynoar (PVDF) mix by mass ratio at 80: 10: 10, with N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent, in stainless steel jar mill with the speed ball milling 4h of 200rpm, the paste slurries that obtain are uniformly coated on the collector Al paper tinsel, then in 60 ℃ vacuum drying chamber the oven dry 20 hours standby.With the hard carbon is negative material, mix at 85: 10: 5 by mass ratio with acetylene black, Kynoar (PVDF), with N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent, in stainless steel jar mill with the speed ball milling 2h of 200rpm, the paste slurries that obtain are uniformly coated on the collector Cu paper tinsel, then in 60 ℃ vacuum drying chamber the oven dry 20 hours standby.With the sulfur electrode is anodal, the hard carbon electrode is a negative pole, Celgrad2300 is a barrier film, 1mol/L bis trifluoromethyl sulfonic acid imide li (LiTFSI)/glycol dimethyl ether (DME)+1, and 3-dioxolane (DOL) (volume ratio 1: 1) is assembled into lithium-sulfur cell for electrolyte.
Battery at first carries out constant current charge with the current density of 50mA/g, and the charging upper voltage limit is 3.5V, and this process is that hard carbon cathode carries out the processing of embedding lithium.Carry out constant-current discharge with the current density of 50mA/g then, the discharge lower voltage limit is 1.0V.Battery carries out charge and discharge cycles with the current density of 50mA/g subsequently, and voltage range is 1.0V ~ 3.0V.The first discharge specific capacity of sulfur electrode is 1063.8mAh/g, and charging and discharging curve is smooth, stable.20 times circulation back specific discharge capacity also remains on 843.2mAh/g, shows excellent cycle performance.
Embodiment 4
With sulphur/carbon nano tube compound material is positive pole, mixes mass percent and be 40% LiNiO 2Mixture and acetylene black, Kynoar (PVDF) mix by mass ratio at 80: 10: 10, with N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent, in stainless steel jar mill with the speed ball milling 4h of 200rpm, the paste slurries that obtain are uniformly coated on the collector Al paper tinsel, then in 60 ℃ vacuum drying chamber the oven dry 20 hours standby.With carbonaceous mesophase spherules (MCMB) is negative material, mix at 85: 10: 5 by mass ratio with acetylene black, Kynoar (PVDF), with N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent, in stainless steel jar mill with the speed ball milling 2h of 200rpm, the paste slurries that obtain are uniformly coated on the collector Cu paper tinsel, then in 60 ℃ vacuum drying chamber the oven dry 20 hours standby.With the sulphur combination electrode is positive pole, and the MCMB electrode is a negative pole, and electrolyte adopts PVDF-HFP and DME-DOL-LiTFSI gel electrolyte, is assembled into lithium-sulfur cell.
Battery at first carries out constant current charge with the current density of 50mA/g, and the charging upper voltage limit is 3.5V, and this process is handled for the MCMB negative pole carries out the embedding lithium.Carry out constant-current discharge with the current density of 50mA/g then, the discharge lower voltage limit is 1.0V.Battery carries out charge and discharge cycles with the current density of 50mA/g subsequently, and voltage range is 1.0V ~ 3.0V.The first discharge specific capacity of sulphur combination electrode is 1194.4mAh/g, has occurred 2 tangible discharge platforms on the discharge curve.20 times circulation back specific discharge capacity also remains on 1018.5mAh/g, and the cycle performance of battery has obtained very big improvement.
Embodiment 5
With sulphur/polyaniline composite material is positive pole, mixes mass percent and be 40% LiMn 1.5Co 0.5O 4, other preparation methods make composite sulfur base electrode material with embodiment 1.The first discharge specific capacity of battery is 1028.3mAh/g, and 20 times circulation back specific discharge capacity also remains on 720.5mAh/g.
Embodiment 6
With sulphur/Pt/Polypyrrole composite material is positive pole, mixes mass percent and be 30% LiMn 1.5Co 0.5O 4, other preparation methods make composite sulfur base electrode material with embodiment 1.The first discharge specific capacity of battery is 1137.6mAh/g, and 20 times circulation back specific discharge capacity also remains on 829.2mAh/g.
Embodiment 7
With sulphur/polythiophene composite material is positive pole, mixes mass percent and be 30% LiMn 1.5Co 0.5O 4, other preparation methods make composite sulfur base electrode material with embodiment 1.The first discharge specific capacity of battery is 1198.5mAh/g, and 20 times circulation back specific discharge capacity also remains on 904.6mAh/g.
Embodiment 8
Is anodal with the sublimed sulfur, mixes mass percent and be 20% Li 2.6Co 0.4N, other preparation methods are with embodiment 2.The first discharge specific capacity of battery is 916.8mAh/g, and 20 times circulation back specific discharge capacity also remains on 603.7mAh/g.
Embodiment 9
With sulphur/cerium oxide composite material is positive pole, mixes mass percent and be 15% Li 2FeO 4, other preparation methods make composite sulfur base electrode material with embodiment 3.The first discharge specific capacity of battery is 1047.1mAh/g, and 20 times circulation back specific discharge capacity also remains on 659.2mAh/g.
Embodiment 10
With sulphur/absorbent charcoal composite material is positive pole, mixes mass percent and be 25% Li 6.5Mn 0.5N 4, other preparation methods make composite sulfur base electrode material with embodiment 4.The first discharge specific capacity of battery is 1134.9mAh/g, and 20 times circulation back specific discharge capacity also remains on 787.3mAh/g.
Embodiment 11
Is anodal with the sublimed sulfur, mixes mass percent and be 20% Li 2.5Fe 0.5N 2, other preparation methods are with embodiment 1.The first discharge specific capacity of battery is 925.8mAh/g, and 20 times circulation back specific discharge capacity also remains on 587.6mAh/g.
Embodiment 12
With sulphur/lanthana composite material is positive pole, mixes mass percent and be 30% Li 2S, other preparation methods make composite sulfur base electrode material with embodiment 3.The first discharge specific capacity of battery is 986.4mAh/g, and 20 times circulation back specific discharge capacity also remains on 601.5mAh/g.
Embodiment 13
With sulphur/Yttria Composite is positive pole, mixes mass percent and be 25% Li 2S, other preparation methods make composite sulfur base electrode material with embodiment 3.The first discharge specific capacity of battery is 1017.4mAh/g, and 20 times circulation back specific discharge capacity also remains on 670.2mAh/g.
Embodiment 14
With sulphur/titanium oxide composite material is positive pole, mixes mass percent and be 20% Li 2S, other preparation methods make composite sulfur base electrode material with embodiment 4.The first discharge specific capacity of battery is 1028.5mAh/g, and 20 times circulation back specific discharge capacity also remains on 706.5mAh/g.

Claims (9)

1. lithium-sulfur cell preparation method, it is characterized in that: described lithium-sulfur cell is to be negative pole with the material with carbon element, is positive pole with elemental sulfur, elemental sulfur compound or sulfur-based compound.
2. a kind of lithium-sulfur cell preparation method as claimed in claim 1 is characterized in that: wherein said rich by percentage to the quality lithium compound is 10～40% as the incorporation of the 3rd utmost point.
3. a kind of lithium-sulfur cell preparation method as claimed in claim 1 is characterized in that: wherein rich lithium compound has the irreversible lithium character of taking off.
4. a kind of lithium-sulfur cell preparation method according to claim 3 is characterized in that: wherein said rich lithium compound is selected from
LiMO 2, wherein M=Co, Ni, Mn, Cu, Cr, Fe;
LiMn 2-xM xO 4, wherein when M=Ni, Co, Cu, 0＜x＜1; When M=Cr, Fe, V, 0＜x＜0.5;
LiNi xM 1-xO 2, wherein M=Co, Mn, Cu, Cr, Fe, V, La, Al, Mg, Ga, Zn, 0＜x＜1;
LiNi xMn yCo zO 2(x+y+z＝1)、LiFePO 4、Li 2FeO 4；
Li 3-xM xN, wherein M=Co, Ni, Cu, Cr, V, 0＜x＜1;
Li 7-xMn xN 4, 0＜x＜1 wherein;
Li 3-xFe xN 2, 0＜x＜1 wherein;
Li 2S, Li 2S 2In a kind of.
5. a kind of lithium-sulfur cell preparation method according to claim 1 is characterized in that: wherein said material with carbon element is selected from the group of graphite, petroleum coke, MCMB, middle phase charcoal fiber, high polymer pyrolytic carbon, carbon nano-tube composition.
6. a kind of lithium-sulfur cell preparation method according to claim 1 is characterized in that: wherein said elemental sulfur is sublimed sulfur or high purity sulphur.
7. a kind of lithium-sulfur cell preparation method according to claim 1 is characterized in that: wherein said elemental sulfur compound is selected from:
Sulphur/carbon material compound, wherein material with carbon element is carbon nano-tube, carbon nano-fiber, active carbon, carbon aerogels, carbon black;
Sulphur/conductive polymer composite, wherein conducting polymer is polyaniline, polypyrrole, polythiophene;
Sulphur/inorganic oxide compound, wherein inorganic oxide is a kind of in yittrium oxide, lanthana, cerium oxide, the titanium oxide.
8. a kind of lithium-sulfur cell preparation method according to claim 1, it is characterized in that: wherein said sulfur-based compound is selected from:
Li 2S n, n 〉=1 wherein;
Organosulfur compound;
Molecular formula is (C 2S x) nCarbon sulphur polymer, x=2.5～10 wherein, n 〉=2.
9. lithium-sulfur cell that makes according to arbitrary described method among the claim 1-8.
CNA2009100851370A 2009-06-02 2009-06-02 Lithium-sulfur battery and preparation method thereof Pending CN101562261A (en)

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WO2014191420A1 (en) * 2013-05-28 2014-12-04 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Alkali metal-sulfur battery with ether as an electrolyte solvent
DE102013209982B4 (en) 2013-05-28 2023-02-16 Technische Universität Dresden Alkaline metal-sulphur battery and method of operating it
CN103560265A (en) * 2013-11-06 2014-02-05 东莞新能源科技有限公司 Lithium ion battery as well as lithium-rich positive piece and preparation method thereof
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CN104681855A (en) * 2015-02-26 2015-06-03 广东烛光新能源科技有限公司 Naked cell, finished cell and preparation method of lithium-sulfur battery
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CN105390663A (en) * 2015-10-16 2016-03-09 广东烛光新能源科技有限公司 Sulfur-containing electrode, lithium-sulfur battery containing sulfur-containing electrode and manufacturing method for lithium-sulfur battery
CN105355876A (en) * 2015-11-07 2016-02-24 合肥国轩高科动力能源有限公司 Preparation method for composite conductive polymer coated with elemental sulfur and applications
CN105529446A (en) * 2016-01-20 2016-04-27 中南大学 Lithium-sulfur battery composite positive electrode material and preparation method and application therefor
CN105609742A (en) * 2016-03-04 2016-05-25 河北工业大学 Positive electrode material for sulfur-based lithium ion battery and preparation method and application of positive electrode material
CN105609742B (en) * 2016-03-04 2018-06-22 河北工业大学 A kind of sulfenyl anode material for lithium-ion batteries and its preparation method and application
CN106299286A (en) * 2016-09-08 2017-01-04 天津大学 A kind of lithium-sulfur cell macromolecule composite positive pole and preparation method
CN106299286B (en) * 2016-09-08 2018-11-30 天津大学 A kind of lithium-sulfur cell macromolecule composite positive pole and preparation method
CN106410262A (en) * 2016-10-24 2017-02-15 东莞市联洲知识产权运营管理有限公司 High-voltage and high-capacity lithium-sulfur battery
CN107221675A (en) * 2017-06-21 2017-09-29 镇江宇神动力能源有限公司 A kind of preparation method of lithium-sulfur cell
CN109713236A (en) * 2017-10-25 2019-05-03 蔚来汽车有限公司 Positive electrode for lithium-sulfur cell and the lithium-sulfur cell comprising it
CN111630693A (en) * 2018-03-16 2020-09-04 株式会社Lg化学 Ceria-carbon-sulfur composite, method for manufacturing the same, and positive electrode and lithium-sulfur battery comprising the same
US11978888B2 (en) 2018-03-16 2024-05-07 Lg Energy Solution, Ltd. Ceria-carbon-sulfur composite, method for preparing same, and positive electrode and lithium-sulfur battery comprising same
CN111630693B (en) * 2018-03-16 2023-12-05 株式会社Lg新能源 Ceria-carbon-sulfur composite, method for producing same, and positive electrode and lithium-sulfur battery comprising same
CN109167045A (en) * 2018-09-12 2019-01-08 肇庆市华师大光电产业研究院 A method of sulfur-based positive electrode material is prepared using mesh structural porous nano lanthanum oxide
CN109167045B (en) * 2018-09-12 2021-07-27 肇庆市华师大光电产业研究院 Method for preparing sulfur-based positive electrode material by applying reticular porous nano lanthanum oxide
CN110061286A (en) * 2019-04-30 2019-07-26 郑州中科新兴产业技术研究院 A kind of lithium ion battery with high energy density and preparation method thereof with prelithiation effect
CN110061286B (en) * 2019-04-30 2021-03-02 郑州中科新兴产业技术研究院 High-energy-density lithium ion battery with pre-lithiation effect and preparation method thereof
CN110828881A (en) * 2019-08-28 2020-02-21 深圳先进技术研究院 Dual-ion battery and preparation method thereof
CN112072067A (en) * 2020-09-18 2020-12-11 北京理工大学 Carbon-sulfur composite positive electrode for lithium-sulfur battery and preparation method thereof
CN112615011A (en) * 2020-12-17 2021-04-06 惠州亿纬锂能股份有限公司 Lithium-sulfur battery negative pole piece, lithium-sulfur battery and preparation method thereof

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