WO2018195837A1

WO2018195837A1 - Metal-sulfur battery and preparation method therefor

Info

Publication number: WO2018195837A1
Application number: PCT/CN2017/082079
Authority: WO
Inventors: 李彦光; 叶华林; 李佩蓉
Original assignee: 苏州大学张家港工业技术研究院
Priority date: 2017-04-26
Filing date: 2017-04-26
Publication date: 2018-11-01

Abstract

Disclosed in the present invention is a metal-sulfur battery. The metal-sulfur battery comprises a positive electrode, a negative electrode, and electrolytes. The negative electrode is made of metal. The positive electrode comprises a transitional metal sulfide, or the positive electrode comprises a sulfur-containing material and a transitional metal material. The electrolytes comprise a liquid electrolyte and a solid electrolyte. The metal-sulfur battery has excellent effect on inhibiting the loss of active materials and on the shuttle effect caused by the dissolution of polysulfides in traditional metal-sulfur batteries. Even through the active substance sulfur exists in the electrolytes in the form of polysulfides, the transitional metal collector can also capture almost all of the polysulfides and make them no longer return to the electrolytes by means of the strong chemical actions of the transitional metal and the polysulfides, and a series of problems caused by the dissolution of the polysulfides is suppressed from the root, and unexpected technical results are obtained.

Description

发明名称：一种金属-硫电池及其制备方法技术领域 Title: A metal-sulfur battery and a preparation method thereof

本发明属于储能技术领域，具体涉及一种金属-硫电池及其制备方法。 The invention belongs to the technical field of energy storage, and particularly relates to a metal-sulfur battery and a preparation method thereof.

背景技术 Background technique

随着锂离子电池向电动汽车、航空、军事等大型领域的发展，锂离子电池的能量密度、功率密度等性能指标需要进一步提高。但是受限于锂离子电池电极材料理论比容量的限制，即使考虑使用更高比容量的三元正极材料和硅碳负极材料，也很难使锂离子电池的能量密度达到 500 Wh kg -1以上。在目前所研究的下一代储能二次电池体中，锂硫电池以其突出的理论能量密度（2567 Wh kg i) 受到了人们的广泛研究。另一方面，锂资源的不断消耗最终也会限制锂硫电池的发展。因此，在大规模智能电网储能上，具有更低成本的其他金属-硫电池（钠硫、钾硫、镁硫、铝硫等）的优势将会更加明显。 With the development of lithium-ion batteries in large fields such as electric vehicles, aviation, and military, the performance indexes such as energy density and power density of lithium-ion batteries need to be further improved. However, limited by the theoretical specific capacity limitation of the lithium ion battery electrode material, even considering the use of a higher specific capacity ternary positive electrode material and a silicon carbon negative electrode material, it is difficult to make the energy density of the lithium ion battery reach 500 Wh kg -1 or more. . Among the next generation of energy storage secondary batteries currently under study, lithium-sulfur batteries have been extensively studied for their outstanding theoretical energy density (2567 Wh kg i). On the other hand, the continuous consumption of lithium resources will eventually limit the development of lithium-sulfur batteries. Therefore, in the large-scale smart grid energy storage, the advantages of other metal-sulfur batteries (sodium sulfur, potassium sulfur, magnesium sulfur, aluminum sulfur, etc.) with lower cost will be more obvious.

然而，采用单质硫作为电极往往会导致一系列无法避免的问题。首先，单质硫以及最终放电产物的电子绝缘性极大地降低了整个电化学反应速率；其次，充放电过程中形成的多硫化物极易溶解在电解液中，并进一步扩散到负极被还原，从而造成多硫化物的穿梭效应；此外，金属负极的不均匀沉积以及与多硫化物的化学反应会导引起负极表面枝晶的生长和多硫化物的侵蚀。所有的这些问题都源自多硫化物的溶解与扩散，从而导致活性物质的不断消耗与损失，最终严重地制约了金属硫电池的实用化。目前，大部分研究都集中于将单质硫包覆在多孔碳里面，从而来提高电极的导电性和减缓多硫化物的溶解与穿梭。但是，这并没有从根本上解决多硫化物的损失问题，只是减缓了这一进程。同吋，也有部分研究聚焦于含硫聚合物，这些含硫聚合物材料虽然也能很好地抑制多硫化物的溶解于穿梭，但是它们往往比容量比较低、动力学脱嵌速度也比较慢，而且在合成方法上也不可避免地需要使用高污染的有机溶剂。因此，很有必要构建一种新的金属 -硫电池体系，来实现高性能金属-硫电池。 However, the use of elemental sulfur as an electrode often leads to a series of unavoidable problems. First, the electronic insulation of elemental sulfur and the final discharge product greatly reduces the overall electrochemical reaction rate; secondly, the polysulfide formed during charge and discharge is easily dissolved in the electrolyte and further diffused to the negative electrode to be reduced, thereby The shuttle effect of polysulfide is caused; in addition, uneven deposition of the metal negative electrode and chemical reaction with polysulfide may cause dendrite growth and polysulfide corrosion on the surface of the negative electrode. All of these problems are caused by the dissolution and diffusion of polysulfides, resulting in the continuous consumption and loss of active substances, which ultimately severely restricts the practical use of metal sulfur batteries. At present, most of the research has focused on coating elemental sulfur in porous carbon to improve the conductivity of the electrode and slow down the dissolution and shuttle of polysulfide. However, this did not fundamentally solve the problem of polysulfide loss, but only slowed down the process. At the same time, some studies have focused on sulfur-containing polymers. Although these sulfur-containing polymer materials can also inhibit the dissolution of polysulfides in shuttles, they tend to have lower specific capacity and slower kinetic deintercalation. Moreover, it is inevitable to use a highly polluting organic solvent in the synthesis method. Therefore, it is necessary to build a new metal-sulfur battery system to achieve a high performance metal-sulfur battery.

技术问题问题的解决方案 technical problem Problem solution

技术解决方案 Technical solution

[0004] 本发明的发明目的是公幵一种金属-硫电池及其制备方法，首次利用过渡金属硫化物及其复合物作为与硫当量的正极材料来设计室温以及高温金属硫电池；利用过渡金属来稳定硫正极。在电化学的环境下，借助过渡金属与硫或充放电中间产物多硫化物之间强烈的化学作用，通过化学成键使电池中的硫以过渡金属硫化物的形式储存在正极，使之不再回归电解液中，从源头上抑制了多硫化物溶出导致的一系列问题，提高电池的容量和循环寿命；过渡金属与多硫化物间的化学作用可以是直接化学反应、化学吸附、化学配位等，可以生成过渡金属硫化物、过渡金属亚硫化物、过渡金属过硫化物、过渡金属-硫配位化合物等 [0004] The object of the present invention is to disclose a metal-sulfur battery and a preparation method thereof, using a transition metal sulfide and a composite thereof as a positive electrode material with sulfur equivalent for the first time to design a room temperature and high temperature metal sulfur battery; Metal to stabilize the sulfur positive electrode. In an electrochemical environment, by the strong chemical interaction between the transition metal and sulfur or the charge and discharge intermediate polysulfide, the sulfur in the battery is stored in the positive electrode as a transition metal sulfide by chemical bonding, so that Returning to the electrolyte, the series of problems caused by the dissolution of polysulfide are suppressed from the source, and the capacity and cycle life of the battery are improved. The chemical interaction between the transition metal and the polysulfide can be direct chemical reaction, chemical adsorption, chemical matching. Bit, etc., can form transition metal sulfides, transition metal sulfites, transition metal persulfides, transition metal-sulfur coordination compounds, etc.

[0005] 为实现上述目的，采用具体的技术方案如下：一种金属-硫电池，包括正极、负极以及电解液；所述负极为金属；所述正极包括过渡金属硫化物；或者所述正极包括含硫材料以及过渡金属材料；所述电解液包括液态电解液和固态电解液。 [0005] In order to achieve the above object, a specific technical solution is adopted as follows: A metal-sulfur battery comprising a positive electrode, a negative electrode and an electrolyte; the negative electrode is a metal; the positive electrode includes a transition metal sulfide; or the positive electrode includes a sulfur-containing material and a transition metal material; the electrolyte includes a liquid electrolyte and a solid electrolyte.

[0006] 上述技术方案中，所述过渡金属硫化物的化学式为 MS _x，其中 x≥3; 所述负极金属包括锂、钠、钾、镁、铝；所述过渡金属包括钛、钒、铁、钴、镍、铜、锌、钼、钨；所述含硫材料为硫单质、负极金属硫化物或者负极金属多硫化物；所述过渡金属材料为单一过渡金属材料或 /和过渡金属合金材料。所述包括过渡金属硫化物的正极还可包括碳基材料；所述过渡金属硫化物、碳基材料的质量比为 1: (0〜2) ；所述碳基材料包括碳黑、碳纳米管、石墨烯、碳纤维或者多孔碳。所述过渡金属材料为粉末、纤维、薄膜、泡沫或者三维多孔结构；所述粉末为微米颗粒、纳米颗粒、纳米线、二维层状纳米片中的一种或几种。 [0006] In the above technical solution, the chemical formula of the transition metal sulfide is MS _x , wherein x≥3; the negative metal includes lithium, sodium, potassium, magnesium, aluminum; the transition metal includes titanium, vanadium, iron , cobalt, nickel, copper, zinc, molybdenum, tungsten; the sulfur-containing material is sulfur elemental, negative metal sulfide or negative metal polysulfide; the transition metal material is a single transition metal material or/and transition metal alloy material . The positive electrode including the transition metal sulfide may further include a carbon-based material; the mass ratio of the transition metal sulfide to the carbon-based material is 1: (0 to 2); the carbon-based material includes carbon black, carbon nanotubes , graphene, carbon fiber or porous carbon. The transition metal material is a powder, a fiber, a film, a foam or a three-dimensional porous structure; the powder is one or more of microparticles, nanoparticles, nanowires, and two-dimensional layered nanosheets.

[0007] 本发明还公幵了一种金属-硫电池的制备方法，包括以下步骤，在碳基材料存在下，或者不在碳基材料存在下，以过渡金属前驱体化合物为原料，制备碳基材料与过渡金属硫化物复合体系或者过渡金属硫化物；然后将所述碳基材料与过渡金属硫化物复合体系或者过渡金属硫化物制备为正极；以金属为负极；然后将所述正极、负极、电解液组装制备金属-硫电池。或者，将过渡金属材料与含硫材料组合制备正极，再与负极、电解液组装制备金属-硫电池；或者将可溶性含硫材料溶于液体电解液后，再与过渡金属材料组合制备正极，再与负极组装制备金属-硫电池。 [0007] The present invention also discloses a method for preparing a metal-sulfur battery, comprising the steps of: preparing a carbon-based material by using a transition metal precursor compound as a raw material in the presence of a carbon-based material or in the absence of a carbon-based material. a material and a transition metal sulfide composite system or a transition metal sulfide; then preparing the carbon-based material and the transition metal sulfide composite system or the transition metal sulfide as a positive electrode; using the metal as a negative electrode; and then the positive electrode, the negative electrode, Electrolyte assembly to prepare a metal-sulfur battery. Or, the transition metal material and The positive electrode is prepared by combining sulfur-containing materials, and then the metal-sulfur battery is assembled by assembling the negative electrode and the electrolyte; or the soluble sulfur-containing material is dissolved in the liquid electrolyte, and then the positive electrode is combined with the transition metal material to prepare the positive electrode, and then assembled with the negative electrode to prepare metal-sulfur. battery.

[0008] 上述技术方案中，所述负极包括锂、钠、钾、镁、铝；所述过渡金属包括钛、钒、铁、钴、镍、铜、锌、钼、钨；所述碳基材料包括碳黑、碳纳米管、石墨烯、碳纤维或者多孔碳；所述电解液包括液态电解液和固态电解液；利用酸性水解法、液相合成法、固相球磨法、溶剂热法或者热分解法制备碳基材料与过渡金属硫化物复合体系或者过渡金属硫化物；在碳基材料存在下，首先将碳基材料与过渡金属前驱体化合物混合，再制备碳基材料与过渡金属硫化物复合体系；所述碳基材料与过渡金属硫化物复合体系的粒径为 1〜10000纳米；所述过渡金属硫化物的粒径为 1〜10000纳米；所述含硫材料为硫单质、负极金属硫化物或者负极金属多硫化物，所述过渡金属材料为粉末、纤维、薄膜、泡沫或者三维多孔结构。 [0008] In the above technical solution, the anode includes lithium, sodium, potassium, magnesium, aluminum; the transition metal includes titanium, vanadium, iron, cobalt, nickel, copper, zinc, molybdenum, tungsten; the carbon-based material Including carbon black, carbon nanotubes, graphene, carbon fiber or porous carbon; the electrolyte includes a liquid electrolyte and a solid electrolyte; using an acidic hydrolysis method, a liquid phase synthesis method, a solid phase ball milling method, a solvothermal method or a thermal decomposition Method for preparing carbon-based material and transition metal sulfide composite system or transition metal sulfide; in the presence of carbon-based material, first mixing carbon-based material with transition metal precursor compound, and preparing carbon-based material and transition metal sulfide composite system The carbon-based material and the transition metal sulfide composite system have a particle diameter of 1 to 10000 nm; the transition metal sulfide has a particle diameter of 1 to 10000 nm; and the sulfur-containing material is a sulfur simple substance and a negative metal sulfide. Or a negative metal polysulfide, the transition metal material being a powder, a fiber, a film, a foam or a three-dimensional porous structure.

[0009] 上述技术方案中，在碳基材料存在下，酸性水解法为，将碳基材料分散在水溶液中，再加入过渡金属前驱物，搅拌均匀后，再逐滴加入酸溶液，反应后，得到碳基材料与过渡金属硫化物复合体系；固相球磨法为，将碳基材料、过渡金属和硫粉按计量比混合均匀，转移到球磨罐中抽真空，再于惰性气体下装配好后，转移至球磨机球磨得到碳基材料与过渡金属硫化物复合体系；液相合成法为将碳基材料均匀地分散在水溶液中，再加入过渡金属前驱物，搅拌均匀后，再逐滴加入活泼金属多硫化物溶液，反应得到碳基材料与过渡金属硫化物复合体系；不在碳基材料存在下，酸性水解法为，向过渡金属前驱物中逐滴加入酸溶液，反应后，得到过渡金属硫化物；固相球磨法为，将过渡金属和硫粉按计量比混合均匀，转移到球磨罐中抽真空，再于惰性气体下装配好后，转移至球磨机球磨得到过渡金属硫化物；液相合成法为将向过渡金属前驱物中逐滴加入活泼金属多硫化物溶液，反应得到过渡金属硫化物；所述粉末为微米颗粒、纳米颗粒、纳米线、二维层状纳米片中的一种或几种。 [0009] In the above technical solution, in the presence of a carbon-based material, the acidic hydrolysis method is: dispersing the carbon-based material in an aqueous solution, adding a transition metal precursor, stirring uniformly, and then adding the acid solution dropwise, after the reaction, A carbon-based material and a transition metal sulfide composite system are obtained; in the solid phase ball milling method, the carbon-based material, the transition metal, and the sulfur powder are uniformly mixed in a metering ratio, transferred to a ball mill tank for vacuuming, and then assembled under an inert gas. Transfer to ball mill for ball mill to obtain carbon-based material and transition metal sulfide composite system; liquid phase synthesis method is to uniformly disperse carbon-based material in aqueous solution, then add transition metal precursor, stir evenly, then add active metal dropwise The polysulfide solution is reacted to obtain a composite system of a carbon-based material and a transition metal sulfide; in the absence of a carbon-based material, the acidic hydrolysis method is: adding an acid solution dropwise to the transition metal precursor, and after the reaction, obtaining a transition metal sulfide The solid phase ball milling method is to mix the transition metal and sulfur powder in a stoichiometric ratio and transfer to a ball mill tank. After vacuuming, and then assembling under inert gas, transfer to a ball mill for ball milling to obtain transition metal sulfide; liquid phase synthesis method is to add a reactive metal polysulfide solution dropwise to the transition metal precursor to obtain transition metal sulfide The powder is one or more of microparticles, nanoparticles, nanowires, and two-dimensional layered nanosheets.

[0010] 本发明进一步公幵了一种金属-硫电池正极材料的制备方法，包括以下步骤，在碳基材料存在下，或者不在碳基材料存在下，以过渡金属前驱体化合物为原料，制备碳基材料与过渡金属硫化物复合体系或者过渡金属硫化物，然后将所述碳基材料与过渡金属硫化物复合体系或者过渡金属硫化物制备为金属-硫电池正极材料；或者将过渡金属材料与含硫材料组合制备正极；或者将可溶性含硫材料溶于液体电解液后，再与过渡金属材料组合制备正极；所述含硫材料为硫单质、负极金属硫化物或者负极金属多硫化物，所述过渡金属材料为过渡金属材料粉末、纤维、薄膜、泡沫或者三维多孔结构。 [0010] The present invention further discloses a method for preparing a metal-sulfur battery positive electrode material, comprising the steps of: using a transition metal precursor compound in the presence of a carbon-based material or in the absence of a carbon-based material Preparing a carbon-based material and a transition metal sulfide composite system or a transition metal sulfide, and then preparing the carbon-based material and the transition metal sulfide composite system or the transition metal sulfide as a metal-sulfur battery cathode material; or The metal material is combined with the sulfur-containing material to prepare the positive electrode; or the soluble sulfur-containing material is dissolved in the liquid electrolyte, and then combined with the transition metal material to prepare the positive electrode; the sulfur-containing material is sulfur elemental substance, negative electrode metal sulfide or negative electrode metal polysulfide The transition metal material is a transition metal material powder, a fiber, a film, a foam or a three-dimensional porous structure.

[0011] 本发明还公幵了一种金属 -硫电池正极材料，由过渡金属硫化物或者碳基材料与过渡金属硫化物复合体系制备得到；或者所述正极包括含硫材料以及过渡金属材料；所述含硫材料为硫单质、负极金属硫化物或者负极金属多硫化物；所述过渡金属包括钛、钒、铁、钴、镍、铜、锌、钼、钨。 [0011] The present invention also discloses a metal-sulfur battery cathode material, which is prepared from a transition metal sulfide or a carbon-based material and a transition metal sulfide composite system; or the cathode includes a sulfur-containing material and a transition metal material; The sulfur-containing material is a sulfur element, a negative electrode metal sulfide or a negative electrode metal polysulfide; and the transition metal includes titanium, vanadium, iron, cobalt, nickel, copper, zinc, molybdenum, tungsten.

[0012] 上述技术方案中，利用酸性水解法、液相合成法、固相球磨法、溶剂热法、热分解法制备过渡金属硫化物或者碳基材料与过渡金属硫化物复合体系；在碳基材料存在下，首先将碳基材料与过渡金属前驱体化合物混合，再制备过渡金属硫化物： [0012] In the above technical solution, the acidic metal hydrolysis method, the liquid phase synthesis method, the solid phase ball milling method, the solvothermal method, the thermal decomposition method for preparing a transition metal sulfide or a carbon-based material and a transition metal sulfide composite system; In the presence of the material, the carbon-based material is first mixed with the transition metal precursor compound to prepare a transition metal sulfide:

[0013] 首先利用相应的过渡金属（V、 Nb、 Ti、 Mo、 W、 Fe、 Co、 Ni等）的前驱体 [0013] First, a precursor of a corresponding transition metal (V, Nb, Ti, Mo, W, Fe, Co, Ni, etc.) is utilized.

，在引入少量基体材料（碳纳米管，石墨烯，碳纤维，多孔碳以及其它各种材料）作为导电添加剂或者碳基的条件下，合成碳基材料与过渡金属硫化物复合体系并制成正电极；然后以金属锂、钠、钾、镁、铝、锌或者铁作为负极，采用酯类或者醚类电解液，构成最终的金属-硫电池体系。过渡金属前驱体化合物可以为含硫过渡金属前驱体化合物，也可以为过渡金属与硫粉混合体系。 , introducing a small amount of matrix material (carbon nanotubes, graphene, carbon fiber, porous carbon and various other materials) as a conductive additive or carbon-based, synthesizing a carbon-based material and a transition metal sulfide composite system and forming a positive electrode Then, using lithium metal, sodium, potassium, magnesium, aluminum, zinc or iron as the negative electrode, an ester or ether electrolyte is used to form the final metal-sulfur battery system. The transition metal precursor compound may be a sulfur-containing transition metal precursor compound or a mixed metal and sulfur powder mixed system.

[0014] 合成过渡金属硫化物的方法为：液相水解法、固相球磨法、溶剂热法、热分解法等。本发明通过简单的一步法，实现过渡金属硫化物和基体材料（碳纳米管，石墨烯，碳纤维，多孔碳以及其它各种材料）形成均匀地复合物结构；最终得到的复合材料既具有较好的离子导电率又具有优越的电子导电性。在碳基存在下，酸性水解法为，将碳基材料分散在水溶液中，再加入过渡金属前驱物，搅拌均匀后，再逐滴加入酸溶液；反应后，得到碳基材料与过渡金属硫化物复合体系；固相球磨法为，将碳基材料、过渡金属和硫粉按计量比混合均匀，转移到球磨罐中抽真空，再于惰性气体比如 Ar气下装配好后，转移至球磨机球磨得到碳基材料与过渡金属硫化物复合体系；液相合成法为将碳基材料均匀地分散在水溶液中，再加入过渡金属前驱物，搅拌均匀后，再逐滴加入活泼金属多硫化物溶液（多硫化锂、多硫化钠、多硫化钾等）；反应得到碳基材料与过渡金属硫化物复合体系；不在碳基存在下，酸性水解法为，向过渡金属前驱物中逐滴加入酸溶液；反应后，得到过渡金属硫化物；固相球磨法为，将过渡金属和硫粉按计量比混合均匀，转移到球磨罐中抽真空，再于 Ar气下装配好后，转移至球磨机球磨得到过渡金属硫化物；液相合成法为将向过渡金属前驱物中逐滴加入活泼金属多硫化物溶液（多硫化锂、多硫化钠、多硫化钾等）；反应得到过渡金属硫化物。下面介绍以碳纳米管作为添加剂为例，具体的合成方法如下： [0014] The method for synthesizing the transition metal sulfide is: a liquid phase hydrolysis method, a solid phase ball milling method, a solvothermal method, a thermal decomposition method, or the like. The invention realizes a transition metal sulfide and a matrix material (carbon nanotubes, graphene, carbon fiber, porous carbon and various other materials) to form a uniform composite structure by a simple one-step method; the finally obtained composite material has better The ionic conductivity in turn has superior electronic conductivity. In the presence of a carbon group, the acidic hydrolysis method is: dispersing the carbon-based material in an aqueous solution, adding a transition metal precursor, stirring uniformly, and then adding the acid solution dropwise; after the reaction, obtaining a carbon-based material and a transition metal sulfide Composite system; solid phase ball milling method, carbon-based material, transition metal and sulfur powder are uniformly mixed according to the metering ratio, transferred to a ball mill tank for vacuuming, and then assembled under an inert gas such as Ar gas, transferred to a ball mill ball mill A carbon-based material and a transition metal sulfide composite system are obtained; in the liquid phase synthesis method, the carbon-based material is uniformly dispersed in an aqueous solution, and then a transition metal precursor is added, and after stirring uniformly, an active metal polysulfide solution is added dropwise ( Lithium polysulfide, sodium polysulfide, potassium polysulfide, etc.; reaction to obtain a carbon-based material and a transition metal sulfide composite system; in the absence of a carbon base, the acidic hydrolysis method is, adding an acid solution dropwise to the transition metal precursor; After the reaction, a transition metal sulfide is obtained; in the solid phase ball milling method, the transition metal and the sulfur powder are uniformly mixed in a metering ratio, transferred to a ball mill tank for vacuuming, and then assembled under Ar gas, and transferred to a ball mill to obtain a transition. Metal sulfide; liquid phase synthesis method is to add a reactive metal polysulfide solution (lithium polysulfide, sodium polysulfide, potassium polysulfide, etc.) to the transition metal precursor; and obtain a transition metal sulfide. The following describes the use of carbon nanotubes as an additive. The specific synthesis method is as follows:

[0015] 酸性水解法：将碳纳米管均匀地分散在水溶液中，利用超声辅助均匀分散后再加入过渡金属前驱物，搅拌均匀后，再缓慢逐滴加入酸溶液；经过充分反应两小吋后，得到最终的渗入碳纳米管的金属硫化物；所述金属盐为金属硫铵盐；所述过渡金属比如钼、钨，最终得到的产物（MoS _X/CNT和 WS _X/CNT) 颗粒的粒径大约为 100〜500纳米。 [0015] Acid hydrolysis method: uniformly disperse the carbon nanotubes in an aqueous solution, and uniformly add the transition metal precursor by ultrasonication, stir evenly, and then slowly add the acid solution dropwise; after fully reacting for two hours Obtaining a final metal sulfide which penetrates into the carbon nanotube; the metal salt is a metal ammonium ammonium salt; the transition metal such as molybdenum, tungsten, and finally obtained product (MoS _X /CNT and WS _X /CNT) particles The diameter is approximately 100 to 500 nm.

[0016] 固相球磨法：将碳纳米管、过渡金属和硫粉按照设定的化学计量比混合均匀，转移到球磨罐中抽真空 2 h，再放置到 Ar气手套箱中搁置 12 h; 在手套箱中装配好后，转移至球磨机里在一定的转速条件下球磨至得到目标产物。所述过渡金属比如为钛、钒、铌，转速为 300-500 rpm，球磨吋间为 20-80 h，最终得到的产物（FeS _x/CNT、 VS _X/CNT和 NbS _X/CNT) 颗粒的粒径大约为 100〜500纳米。 [0016] solid phase ball milling method: carbon nanotubes, transition metal and sulfur powder are uniformly mixed according to a set stoichiometric ratio, transferred to a ball mill tank for 2 hours, and then placed in an Ar gas glove box for 12 hours; After assembly in the glove box, transfer to a ball mill and ball-mill at a certain speed to obtain the desired product. The transition metal is, for example, titanium, vanadium, niobium, rotating at 300-500 rpm, ball-milling between 20-80 h, and finally obtained products (FeS _x /CNT, VS _X /CNT and NbS _X /CNT) particles The particle size is approximately 100 to 500 nm.

[0017] 液相合成法：将碳纳米管均匀地分散在水溶液中，利用超声辅助均匀分散后再加入过渡金属前驱物，搅拌均匀后，再缓慢逐滴加入活泼金属多硫化物溶液（多硫化锂、多硫化钠、多硫化钾等）；经过充分反应两小吋后，得到最终渗入碳纳米管的过渡金属硫化物；所述金属盐为金属硝酸盐、金属醋酸盐、金属硫酸盐或者金属氯化盐，所述过渡金属比如为铁、钴、镍；最终得到的产物（FeS X/CNT、 CoS _X/CNT和 NiS _X/CNT) 颗粒的粒径大约为 1〜10000纳米。 [0017] Liquid phase synthesis method: uniformly disperse carbon nanotubes in an aqueous solution, use ultrasonic to assist uniform dispersion, and then add a transition metal precursor, stir evenly, and then slowly add a live metal polysulfide solution (multi-vulcanization) Lithium, sodium polysulfide, potassium polysulfide, etc.; after two hours of sufficient reaction, a transition metal sulfide finally infiltrating into the carbon nanotubes is obtained; the metal salt is a metal nitrate, a metal acetate, a metal sulfate or The metal chloride salt is, for example, iron, cobalt or nickel; and the finally obtained products (FeS X/CNT, CoS _X /CNT and NiS _X /CNT) particles have a particle diameter of about 1 to 10,000 nm.

[0018] 上述所有合成方法均采用室温条件一锅法合成；所采用的碳纳米管与金属的摩尔比可以在合成的过程中进行调控。原料的来源比较丰富易得；而且碳纳米管的加入量非常少，只占最终产物质量分数的 10%左右；并且，碳纳米管还可以采用比较便宜易得的碳纤维、无定形碳黑、科琴黑来代替。它们具有良好的导电性和巨大的比表面积，能够有效保证所合成材料优异的导电性以及与电解液良好的相容性。此外，整个合成过程没有采用高污染的强酸、强碱和其他有机溶齐 ij，整个合成过程无污染，符合绿色合成的要求。 [0018] All of the above synthetic methods are one-pot synthesis using room temperature conditions; the molar ratio of carbon nanotubes to metal used can be adjusted during the synthesis process. The source of raw materials is relatively abundant and easy to obtain; The amount of addition is very small, only about 10% of the final product mass fraction; and, carbon nanotubes can also be replaced by carbon fiber, amorphous carbon black, Ketjen black which is relatively cheap and easy to obtain. They have good electrical conductivity and a large specific surface area, which can effectively ensure the excellent conductivity of the synthesized materials and good compatibility with the electrolyte. In addition, the entire synthetic process does not use highly polluted strong acids, strong alkalis and other organic solvents, and the entire synthetic process is non-polluting, in line with the requirements of green synthesis.

[0019] 特别地，所有采用的合成方案均没有采用表面活性剂来有目的地控制材料的形貌和尺寸；没有使用高污染、难处理的有机溶剂；没有采用高能耗的高温、高压合成条件。因此所有合成方案均能够容易地大规模化生产。 [0019] In particular, all of the synthetic schemes employed do not use surfactants to purposefully control the morphology and size of the material; do not use highly contaminated, refractory organic solvents; do not employ high-energy, high-temperature, high-pressure synthesis conditions . Therefore, all synthetic schemes can be easily mass-produced.

[0020] 本发明中，过渡金属硫化物、碳基材料的质量比为 1:0〜2；在加大碳纳米管的用量下，可以得到由碳纳米管和过渡金属硫化物相互交织的复合物，即碳基材料与过渡金属硫化物复合体系，这种复合物作为电极具有非常强的柔韧性和机械性能。其中酸性水解法和液相合成法在反应结束后，用去离子水洗涤掉杂质后，采用醇比如异丙醇进行超声分散；得到的分散液进行抽滤，低温烘干后可以得到自支撑、高密度、厚度可控的正极薄膜。这种薄膜可以直接用作电极来制备电池，而无需后续的添加导电剂和粘结剂进行制备正极；固相球磨法得到的固体混合物可以直接分散到醇比如异丙醇中，进行抽滤，低温烘干得到同样的薄膜电极。抽滤的滤纸采用疏水 200 [0020] In the present invention, the mass ratio of the transition metal sulfide and the carbon-based material is 1:0~2; when the amount of the carbon nanotubes is increased, a composite of carbon nanotubes and transition metal sulfides intertwined can be obtained. The compound, that is, a carbon-based material and a transition metal sulfide composite system, which has very strong flexibility and mechanical properties as an electrode. In the acidic hydrolysis method and the liquid phase synthesis method, after the reaction is finished, the impurities are washed away with deionized water, and then ultrasonically dispersed by using an alcohol such as isopropyl alcohol; the obtained dispersion is subjected to suction filtration, and can be self-supported after being dried at a low temperature. High-density, thickness-controlled positive electrode film. The film can be directly used as an electrode to prepare a battery without the need to add a conductive agent and a binder to prepare a positive electrode; the solid mixture obtained by solid phase ball milling can be directly dispersed into an alcohol such as isopropyl alcohol for suction filtration. The same thin film electrode was obtained by low temperature drying. Filtered filter paper with hydrophobic 200

nm孔径的有机系滤膜，低温烘干温度为 60°C。整个过程简单可控，而且抽滤后的溶剂仍然可以再进行回收利用。本发明制备的过渡金属硫化物或者碳基材料与过渡金属硫化物复合体系也可以与粘接剂一起研磨、涂覆、干燥成片，作为电极。 The organic membrane of the nm pore size has a low temperature drying temperature of 60 °C. The entire process is simple and controllable, and the filtered solvent can still be recycled. The transition metal sulfide or carbon-based material and transition metal sulfide composite system prepared by the present invention may also be ground, coated, and dried together with a binder to form an electrode.

[0021] 本发明的过渡金属硫化物的硫含量可以通过减少添加剂的惨入量，加大硫源的用量以及采用相对质量更小的过渡金属来进一步提高。根据实施例，产品具体的硫含量可以通过热重分析得出，而且可以控制到 80%以上。另外，本发明得到的最终产物并不是过渡金属硫化物和碳基材料简单地混合在一起，而是碳基材料比如碳纳米管完全均匀地渗入到过渡金属硫化物之间；或者与过渡金属硫化物紧密地相互交织在一起形成具有一定柔韧性和机械性能的三维结构。碳基材料的引入，不仅仅提高了材料的导电率，而且还有效地防止了合成过程中过渡金属硫化物的团聚。相比传统的单质硫电极，本发明公幵的过渡金属硫化物中的硫是以结合态的形式存在的。因此，在整个循环过程中，硫始终与过渡金属原子以结合态的形式存在，从而有效地避免了多硫化物的生成，本发明利用过渡金属硫化物设计的新型金属-硫电池由于避免了多硫化物在电解液中的溶解与扩散，从而能展现出更加优越的电池性能。因此，本发明还公幵了过渡金属硫化物在制备金属硫电池中的应用，以及在制备金属硫电池正极材料中的应用。另外，现有的金属硫电池比如锂硫电池均采用醚类电解液，醚类电解液往往沸点低，极易挥发；一旦在高温条件下（>50°C) 工作，电池就会在充放电的过程中产气，进而造成电池潜在的安全问题。一般而言，高温锂离子电池均采用难挥发的酯类电解液，但是酯类电解液极易被多硫化物亲核进攻，从而导致电解液的失效和整个硫活性质量的迅速消耗。因此，传统的单质硫电极是无法在酯类电解液中工作的。本发明克服了现有技术偏见，提出的过渡金属硫化物及碳基材料与过渡金属硫化物复合体系电极在循环过程中并没有产生多硫化物，能够突破醚类电解液的限制，并能成功地在酯类电解液中运行，从而实现高温金属-硫电池，取得了意想不到的技术效果。 [0021] The sulfur content of the transition metal sulfide of the present invention can be further improved by reducing the amount of additives, increasing the amount of sulfur source, and using a transition metal having a relatively small mass. According to an embodiment, the specific sulfur content of the product can be obtained by thermogravimetric analysis and can be controlled to over 80%. In addition, the final product obtained by the present invention is not simply mixed with a transition metal sulfide and a carbon-based material, but a carbon-based material such as carbon nanotubes completely infiltrated into the transition metal sulfide; or with a transition metal sulfide The objects are closely intertwined to form a three-dimensional structure with certain flexibility and mechanical properties. The introduction of carbon-based materials not only improves the electrical conductivity of the material, but also effectively prevents the transition during the synthesis process. Agglomeration of metal sulfides. The sulfur in the transition metal sulfide of the present invention is present in a bound state compared to a conventional elemental sulfur electrode. Therefore, sulfur is always present in a combined state with the transition metal atoms throughout the cycle, thereby effectively avoiding the formation of polysulfides, and the novel metal-sulfur battery designed by the transition metal sulfide of the present invention avoids many The dissolution and diffusion of sulfides in the electrolyte can exhibit superior battery performance. Therefore, the present invention also discloses the use of transition metal sulfides in the preparation of metal sulfur batteries, and in the preparation of metal sulfur battery cathode materials. In addition, existing metal sulfur batteries, such as lithium-sulfur batteries, use ether electrolytes, which tend to have a low boiling point and are extremely volatile; once operated under high temperature conditions (>50 ° C), the battery will be charged and discharged. The process of producing gas, which in turn causes potential safety problems in the battery. In general, high-temperature lithium-ion batteries use a non-volatile ester electrolyte, but the ester electrolyte is easily attacked by polynuclear nucleophiles, resulting in electrolyte failure and rapid consumption of the entire sulfur activity. Therefore, the conventional elemental sulfur electrode cannot work in the ester electrolyte. The invention overcomes the prior art prejudice, and the proposed transition metal sulfide and carbon-based material and the transition metal sulfide composite system electrode do not produce polysulfide during the cycle, can break through the limitation of the ether electrolyte, and can succeed. The operation is carried out in an ester electrolyte to realize a high-temperature metal-sulfur battery, and an unexpected technical effect is obtained.

[0022] 本发明中的过渡金属材料可以在电池组装和循环过程中与硫发生反应，并以硫化物的形式固硫。其中过渡金属的辅助原理为：在金属-硫电池在充放电过程中，借助过渡金属与多硫化物强烈的化学作用，过渡金属可以和硫或金属-硫的充放电过程中产生的一系列多硫化物发生反应，并以过渡金属硫化物的形式储存在正极或者集流体，使之不再回归电解液中，从源头上抑制了多硫化物溶出导致的一系列问题，提高电池的容量和循环寿命。 [0022] The transition metal material of the present invention can react with sulfur during battery assembly and recycling, and fix sulfur in the form of a sulfide. The auxiliary principle of the transition metal is as follows: In the process of charge and discharge of the metal-sulfur battery, a strong series of chemical interactions between the transition metal and the polysulfide, the transition metal can be combined with the sulfur or metal-sulfur charge and discharge process. The sulfide reacts and is stored in the form of a transition metal sulfide in the positive electrode or the current collector so that it does not return to the electrolyte, which suppresses a series of problems caused by the dissolution of polysulfide from the source, and improves the capacity and circulation of the battery. life.

[0023] 本发明采用过渡金属材料包括单一过渡金属本身或合金过渡金属与含硫材料制成复合型硫正极材料，通过制浆、涂膜、烘干等常用的电池组装工艺组装电池，可应用于液体电解液电池和全固态电池。在电池循环过程中，存在于复合正极材料中的过渡金属可以和硫或金属-硫的充放电过程中产生的一系列多硫化物发生反应，由此将这些硫以过渡金属的形式固定在正极材料中继续参与之后的电池循环。过渡金属材料与含硫材料混合制成复合型硫正极材料的方法可以是直接混合、球磨混合、硫高温熔融混合等。在放电过程中，在负极的金属被电化学氧化，形成金属离子，金属离子穿过隔膜到达正极，还原 s ₈分子，生成多硫化物，正极材料中的过渡金属和硫或金属-硫的充放电过程中产生的一系列多硫化物发生反应，参与接下来的充放电过程；充电过程，金属离子离幵正极回到负极被还原成金属沉积。 [0023] The present invention adopts a transition metal material including a single transition metal itself or an alloy transition metal and a sulfur-containing material to form a composite sulfur cathode material, and assembles a battery through a common battery assembly process such as pulping, coating, drying, etc., and can be applied. For liquid electrolyte batteries and all solid state batteries. During the battery cycle, the transition metal present in the composite positive electrode material can react with a series of polysulfides generated during the charging and discharging of sulfur or metal-sulfur, thereby fixing the sulfur in the form of a transition metal to the positive electrode. The material continues to participate in the subsequent battery cycle. The method for mixing the transition metal material and the sulfur-containing material to form the composite sulfur cathode material may be direct mixing, ball milling mixing, sulfur high-temperature melt mixing, and the like. During the discharge process, the metal at the negative electrode is charged Chemical oxidation, formation of metal ions, metal ions passing through the diaphragm to the positive electrode, reduction of s ₈ molecules, formation of polysulfide, transition metal in the positive electrode material and a series of polysulfide generation during the charging and discharging process of sulfur or metal-sulfur The reaction participates in the next charge and discharge process; during the charging process, the metal ions are returned to the negative electrode and returned to the negative electrode to be reduced to metal deposition.

[0024] 本发明还公幵了一种制备方法与传统金属 -硫电池的电池结构不同，本发明设计了一种特殊的金属-硫电池结构，将正极材料溶于电解液中，电池正极集流体上附载过渡金属或直接将纤维、薄膜、泡沫或者三维多孔结构的过渡金属直接作为正极集流体集流体。在电池组装和循环的过程中，过渡金属与电解液中的含硫材料发生化学或电化学反应，使弥漫在电解液中的含硫材料以过渡金属硫化物的形式固定在集流体表面，并以过渡金属硫化物作为活性物质参与之后的电池循环。过渡金属与含硫材料间的化学作用可以是化学吸附、直接化学反应、化学配位等。在放电过程中，在负极的金属被电化学氧化，形成金属离子，金属离子穿过隔膜到达正极，还原过渡金属集流体表面生长的过渡金属硫化物，最终在正极生成过渡金属和金属硫化物；在充电过程的逆过程，过渡金属得电子被氧化生成过渡金属硫化物，负极金属离子离幵正极回到负极被还原成金属沉积。 [0024] The present invention also discloses a preparation method different from the battery structure of a conventional metal-sulfur battery. The present invention designs a special metal-sulfur battery structure, which dissolves the positive electrode material in the electrolyte, and the battery positive electrode set The transition metal is carried on the fluid or the transition metal of the fiber, film, foam or three-dimensional porous structure is directly used as the positive current collector current collector. During the assembly and recycling of the battery, the transition metal chemically or electrochemically reacts with the sulfur-containing material in the electrolyte, so that the sulfur-containing material diffused in the electrolyte is fixed on the surface of the current collector in the form of transition metal sulfide, and The transition metal sulfide is used as an active substance to participate in the subsequent battery cycle. The chemical interaction between the transition metal and the sulfur-containing material may be chemical adsorption, direct chemical reaction, chemical coordination, and the like. During the discharge process, the metal in the negative electrode is electrochemically oxidized to form a metal ion, the metal ion passes through the separator to reach the positive electrode, and the transition metal sulfide grown on the surface of the transition metal current collector is reduced, and finally a transition metal and a metal sulfide are formed on the positive electrode; In the reverse process of the charging process, the electrons of the transition metal are oxidized to form a transition metal sulfide, and the negative electrode metal ions are returned to the negative electrode and returned to the negative electrode to be reduced to metal deposition.

发明的有益效果 Advantageous effects of the invention

有益效果 Beneficial effect

[0025] 由于上述技术方案的运用，本发明与现有技术相比具有如下优点： [0025] Due to the use of the above technical solutions, the present invention has the following advantages over the prior art:

[0026] 1、本发明首次提出采用过渡金属硫化物作为与硫当量的正极材料来构筑室温乃至高温金属硫电池，比如锂硫和钠硫电池，实现金属硫电池的长寿命和高能量密度。 [0026] 1. The present invention first proposes the use of transition metal sulfide as a positive electrode material with sulfur equivalent to construct a room temperature or even a high temperature metal sulfur battery, such as a lithium sulfur and a sodium sulfur battery, to achieve a long life and high energy density of a metal sulfur battery.

[0027] 2、本发明公幵的金属硫电池有效地避免了中间产物多硫化物的形成，从而与传统的硫正极电池相比，有着更优越的比容量、倍率性能和循环性能；同吋也就意味着这种新型金属-硫电池具有更高的功率密度、能量密度和使用寿命。 [0027] 2. The metal sulfur battery of the present invention effectively avoids the formation of intermediate polysulfide, thereby having superior specific capacity, rate performance and cycle performance compared with the conventional sulfur positive electrode; This means that this new metal-sulfur battery has higher power density, energy density and service life.

[0028] 3、本发明公幵的正极材料不仅适用于醚类电解液，更适用于难挥发的酯类电解液，从而能够实现高温金属-硫电池，克服了现有技术偏见，因此本发明公幵的能够使电池在一些热带地区以及高温环境中使用，从而极大地提高了金属-硫电池的应用潜力。 [0028] 3. The positive electrode material of the present invention is applicable not only to ether electrolytes, but also to hardly volatile ester electrolytes, thereby enabling high temperature metal-sulfur batteries, overcoming the prior art bias, and thus the present invention The public can make the battery use in some tropical regions as well as high temperature environment, which greatly improves the metal-sulfur The application potential of the battery.

[0029] 4、本发明所制备的过渡金属辅助的金属 -硫电池对于抑制传统金属 -硫电池中多硫化物溶出所导致的活性物质损失以及穿梭效应有极其优异的效果；即使活性物质硫全部以多硫化物的形式存在于电解液中，通过过渡金属与多硫化物强烈的化学作用，过渡金属集流体也能捕获几乎全部的多硫化物，并使之不再回归电解液中，从源头上抑制了多硫化物溶出导致的一系列问题；取得了意想不到的技术效果。 [0029] 4. The transition metal-assisted metal-sulfur battery prepared by the invention has extremely excellent effects for suppressing active material loss and shuttle effect caused by dissolution of polysulfide in a conventional metal-sulfur battery; In the form of polysulfide in the electrolyte, the transition metal collector can capture almost all of the polysulfide by the strong chemical action of the transition metal and polysulfide, and it will not return to the electrolyte, from the source. A series of problems caused by the dissolution of polysulfide are suppressed; an unexpected technical effect is obtained.

[0030] 5、本发明公幵的过渡金属硫化物及其复合物的制备方法简单、原料来源广泛、价格低廉，大大降低了电池的制造成本；而且应用广泛，非常有利于电池工业的发展。 [0030] 5. The transition metal sulfides and composites thereof of the present invention have simple preparation methods, wide sources of raw materials, low prices, and greatly reduced the manufacturing cost of the battery; and are widely used, which is very advantageous for the development of the battery industry.

对附图的简要说明 Brief description of the drawing

附图说明 DRAWINGS

[0031] 图 1为实施例一的电极不同过渡金属硫化物、碳基材料质量比的循环稳定性曲线对比图； 1 is a comparison diagram of cycle stability curves of mass transition ratios of different transition metal sulfides and carbon-based materials of the electrode of the first embodiment;

[0032] 图 2为实施例一的 MoS ₃/CNT电极在高温 55°C，电流密度为 100 mA/g条件下的恒电流充放电曲线图； 2 is a graph showing a constant current charge and discharge of a MoS ₃ /CNT electrode of Example 1 at a high temperature of 55 ° C and a current density of 100 mA / g;

[0033] 图 3为实施例一的 MoS ₃/CNT电极在高温 55°C，电流密度为 1 A/g条件下的循环稳定性曲线图； 3 is a cycle stability graph of the MoS ₃ /CNT electrode of Example 1 under the conditions of a high temperature of 55 ° C and a current density of 1 A / g;

[0034] 图 4为实施例一的 MoS ₃/CNT的热重分析图； 4 is a thermogravimetric analysis diagram of MoS ₃ /CNT of Example 1;

[0035] 图 5为实施例一的 MoS ₃电极在不同碳基材料（碳纳米管、石墨烯、以及多孔碳[0035] FIG. 5 is a view showing a MoS ₃ electrode of Example 1 in different carbon-based materials (carbon nanotubes, graphene, and porous carbon)

) 复合条件下与商业硫粉电极的循环稳定性曲线对比图； a comparison of cycle stability curves with commercial sulfur powder electrodes under combined conditions;

[0036] 图 6为实施例二的 TiS ₄/CNT电极的恒电流充放电曲线图； 6 is a graph showing a constant current charge and discharge of a TiS ₄ /CNT electrode of Embodiment 2; [0036] FIG.

[0037] 图 7为实施例三的 CoS ₅/CNT电极的恒电流充放电曲线图； 7 is a graph showing a constant current charge and discharge of a CoS ₅ /CNT electrode of Example 3;

[0038] 图 8为实施例一、二、三中不含炭基材料条件下所合成的 MoS ₃、 TiS 4 ^ CoS ₅ 的 XRD图谱； 8 is an XRD pattern of MoS ₃ and TiS 4 ^ CoS ₅ synthesized in the absence of a carbon-based material in Examples 1, 2, and 3;

[0039] 图 9为实施例四中的过渡金属铜辅助的锂硫电池的循环圈数-比容量曲线图； [0040] 图 10为实施例五中的过渡金属钒辅助的锂硫电池的循环圈数-比容量曲线图； [0041] 图 11为实施例六中的过渡金属钼辅助的钠硫电池的循环圈数-比容量曲线图； [0042] 图 12为实施例七中的过渡金属镍辅助的锂硫电池的循环圈数-比容量曲线图； [0043] 图 13为实施例八中的过渡金属铜辅助的高负载的半液流型锂硫电池的循环圈数 -比容量曲线图； 9 is a cycle number-specific capacity curve of a transition metal copper-assisted lithium-sulfur battery in Embodiment 4; [0040] FIG. 10 is a cycle of a transition metal vanadium-assisted lithium-sulfur battery in Embodiment 5.圈数-specific capacity graph; [0041] FIG. 11 is a cycle number-specific capacity curve of a transition metal molybdenum-assisted sodium-sulfur battery in the sixth embodiment; 12 is a cycle number-specific capacity curve of a transition metal nickel-assisted lithium-sulfur battery in Embodiment 7; [0043] FIG. 13 is a transition metal copper-assisted high-load half-liquid in Embodiment 8. Cycle number-specific capacity curve of a flow type lithium-sulfur battery;

[0044] 图 14为实施例九中的过渡金属铜辅助的钠硫电池的循环圈数-比容量曲线图； [0045] 图 15为对比例一中的没有过渡金属辅助的锂硫电池的循环圈数-比容量曲线图 14 is a cycle number-specific capacity curve of a transition metal copper-assisted sodium-sulfur battery in Embodiment 9; [0045] FIG. 15 is a cycle of a lithium-sulfur battery without a transition metal assist in Comparative Example 1. Number of turns - specific capacity curve

[0046] 图 16为对比例一与实施例七中电池循环后的隔膜对比图。 16 is a comparison view of the separator of Comparative Example 1 and the battery after the cycle of Example 7. [0046] FIG.

本发明的实施方式 Embodiments of the invention

[0047] 本实施例将过渡金属硫化物及碳基材料与过渡金属硫化物复合体系直接作为电池正极来应用于金属 -硫电池中。 [0047] In this embodiment, a transition metal sulfide and a carbon-based material and a transition metal sulfide composite system are directly used as a battery positive electrode in a metal-sulfur battery.

[0048] 实施例一 MoS ₃/CNT正极材料的制备（酸性水解法） [Example 1] Preparation of MoS ₃ /CNT cathode material (acid hydrolysis method)

[0049] 材料合成：往 250 mL的圆底烧瓶中加入 40 mL含 1 mmol四硫钼酸铵的水溶液，在磁力搅拌下充分混合均匀；然后再往里加入 40mL含 12 mg分散好的碳纳米管水溶液，充分搅拌 20 min并辅以超声 10 min形成均匀的混合溶液。在磁力搅拌的条件下，往所得到的混合溶液中缓慢加入 1 [0049] Material Synthesis: Add 40 mL of an aqueous solution containing 1 mmol of ammonium tetrathiomolybdate to a 250 mL round bottom flask, and mix well under magnetic stirring; then add 40 mL of 12 mg of dispersed carbon nanoparticle. The tube was stirred for 20 min and supplemented with ultrasound for 10 min to form a homogeneous mixed solution. Under the condition of magnetic stirring, slowly add 1 to the obtained mixed solution.

mol/L的稀 HC1，直到最后混合溶液的 pH值在 3左右。继续充分反应两个小吋后，转移到 50 mL离心管中进行离心分离、去离子水洗涤 3次，再液氮冻干进行冷冻干燥。最终得到的黑色粉末在 Ar保护下 200°C退火 2 h形成最终的产物，过渡金属硫化物、碳纳米管的质量比为 1:0.1，更换碳材料的比例可以得到不同质量比的过渡金属硫化物、碳纳米管复合体系；不加碳纳米管可得到过渡金属硫化物。 Mol/L of dilute HC1 until the pH of the final mixed solution is around 3. After continuing to fully react the two small crucibles, transfer them to a 50 mL centrifuge tube for centrifugation, deionized water for 3 times, and then freeze-dried with liquid nitrogen for freeze drying. The finally obtained black powder is annealed at 200 ° C for 2 h under Ar protection to form the final product. The mass ratio of transition metal sulfide to carbon nanotube is 1:0.1, and the ratio of carbon materials can be changed to obtain transition metal sulfide of different mass ratios. Material, carbon nanotube composite system; transition metal sulfide can be obtained without adding carbon nanotubes.

[0050] 电极的制备：按质量比为 8:1:1称量活性物质、导电剂（Super P) 和粘接剂聚偏二氟乙烯（PVDF) 充分球磨混合，然后在适量的 NMP溶剂中调浆料至粘稠状后，将其均匀地涂布在涂炭铝箔上。最后在真空干燥箱中 120°C真空干燥 12小吋；之后取出，进行碾压和切片备用。 [0050] Preparation of the electrode: The active substance, the conductive agent (Super P) and the binder polyvinylidene fluoride (PVDF) are sufficiently ball-milled at a mass ratio of 8:1:1, and then mixed in an appropriate amount of NMP solvent. After the slurry was viscous, it was uniformly coated on a carbon coated aluminum foil. Finally, it was vacuum dried in a vacuum oven at 120 ° C for 12 hours; then taken out, crushed and sliced for use.

[0051] 电池的制备：为了避免空气和水蒸气对电池的影响，整个组装过程在充满氩气 [0051] Preparation of the battery: In order to avoid the influence of air and water vapor on the battery, the entire assembly process is filled with argon gas.

(水氧含量小于 0.1 ppm) 的手套箱内完成。将工作电极、 PE多孔膜隔膜，作为对电极的金属锂片以及电解液，按正极壳-正极片-电解液 -隔膜 -电解液-垫片-集电器 -弹萤片-负极壳的顺序装入标准 CR2032型扣式电池，组装完成后从手套箱中取出，搁置 12个小吋后进行测试。采用 l mol/L双三氟甲烷磺酰亚胺锂的 1,3- 二氧戊环和乙二醇二甲醚（体积比为 1:1) 溶液作为电解液。 Completed in a glove box (water oxygen content less than 0.1 ppm). The working electrode, the PE porous membrane separator, the lithium metal sheet as the counter electrode, and the electrolyte, according to the cathode shell-positive sheet-electrolyte-separator-electrolyte-gasket-set The electrical-elastic-nano-shell was loaded into the standard CR2032 button cell. After assembly, it was taken out of the glove box and left for 12 small tests. A solution of 1,3-dioxolane and ethylene glycol dimethyl ether (1:1 by volume) of 1 mol/L lithium bistrifluoromethanesulfonimide was used as the electrolyte.

[0052] 电化学性能测试：电池的性能测试均采用恒电流充放电的测试方法。通过在 L AND八通道电池测试***上设定上限电压为 3 V，下限电压 1.2 V；进而获得所测电池的循环性能、充放电曲线、材料比容量、库伦效率。所有的测试均在室温或者 55°C高温条件下测试；测试结果见图 1至图 3。 [0052] Electrochemical performance test: The performance test of the battery adopts the test method of constant current charge and discharge. The upper limit voltage is set to 3 V and the lower limit voltage is 1.2 V on the L AND eight-channel battery test system. The cycle performance, charge and discharge curve, material specific capacity, and coulombic efficiency of the measured battery are obtained. All tests were tested at room temperature or at 55 ° C; the test results are shown in Figures 1 through 3.

[0053] 图 1为上述电极在不同过渡金属硫化物、碳基材料的质量比（1:0、 1:0.1、 1:0.2 ) 条件下的循环稳定性曲线对比图（所有电池比容量均以电极中硫的质量计算 ) ；由图 1可以得出，引入碳基材料会显著提高电极材料的性能。 1 is a comparison diagram of cycle stability curves of the above electrodes under different mass ratios of transition metal sulfides and carbon-based materials (1:0, 1:0.1, 1:0.2) (all battery specific capacities are The mass of sulfur in the electrode is calculated. From Figure 1, it can be concluded that the introduction of carbon-based materials can significantly improve the performance of the electrode material.

[0054] 由图 2可以得出， MoS ₃/CNT电极在 55°C高温下展现出〜 2 V的工作电压和〜 1300 mAh/g的比容量。由图 3可以得出， MoS ₃/CNT电极在 55°C高温下循环 100圈后仍然保持着接近 90%的容量保持率。碳基材料的质量为过渡金属硫化物的 10%。 [0054] It can be seen from FIG. 2 that the MoS ₃ /CNT electrode exhibits an operating voltage of 〜2 V and a specific capacity of ~1300 mAh/g at a high temperature of 55 °C. It can be seen from Fig. 3 that the MoS ₃ /CNT electrode still maintains a capacity retention ratio close to 90% after circulating 100 times at a high temperature of 55 °C. The mass of the carbon-based material is 10% of the transition metal sulfide.

[0055] 图 4为上述合成的 MoS ₃/CNT的热重分析（TGA) 图谱；由图可计算出 MoS ₃ 4 is a thermogravimetric analysis (TGA) map of the above synthesized MoS ₃ /CNT; MoS ₃ can be calculated from the graph

/CNT电极材料中的硫含量约为 45.6%; 其它复合物按照同样放入方法得到产物的硫含量。图 5为 MoS ₃电极在不同碳基材料（碳纳米管、石墨烯、以及多孔碳）复合条件下与商业硫粉电极的循环稳定性曲线对比图（所有电池比容量均以电极中硫的质量计算）。 The sulfur content in the /CNT electrode material was about 45.6%; the other compounds were obtained in the same manner as the sulfur content of the product. Figure 5 is a comparison of the cycle stability curves of MoS ₃ electrodes with commercial sulfur powder electrodes under different carbon-based materials (carbon nanotubes, graphene, and porous carbon) (all cell specific capacities are based on the quality of sulfur in the electrode). Calculation).

[0056] 实施例二 TiS ₄/CNT正极材料的制备（固相球磨法） [Example 2] Preparation of TiS ₄ /CNT cathode material (solid phase ball milling method)

[0057] 将 0.176 g碳纳米管、 0.48 g金属钛粉和 1.28 g硫粉按照设定的化学计量比混合均匀，转移到球磨罐中抽真空 2 h，再放置到 Ar气手套箱中搁置 12 h; 在手套箱中装配好后，转移至球磨机里以 500 rpm的转速条件下球磨 80 [0057] 0.176 g of carbon nanotubes, 0.48 g of titanium metal powder and 1.28 g of sulfur powder were uniformly mixed according to a set stoichiometric ratio, transferred to a ball mill tank for 2 h, and placed in an Ar gas glove box for 12 hours. h; After assembly in the glove box, transfer to the ball mill at a speed of 500 rpm.

h。最终得到的产物 TiS ₄/CNT，过渡金属硫化物、碳基材料的质量比约为 1:0.1。 h. The mass ratio of the finally obtained product TiS ₄ /CNT, transition metal sulfide and carbon-based material is about 1:0.1.

[0058] 其中，电极的制备及电池的组装同实施例一，测试区间在 1.5-3.0 V；测试结果见图 6。由图 6可以得出， TiS ₄/CNT电极展现出〜 2.1 V的工作电压和~860 mAh/g 的比容量，说明本发明公幵的金属硫电池具备优异的电池容量。 [0058] wherein, the preparation of the electrode and the assembly of the battery are the same as in the first embodiment, the test interval is 1.5-3.0 V; the test result is shown in FIG. 6. It can be seen from Fig. 6 that the TiS ₄ /CNT electrode exhibits an operating voltage of ~2.1 V and a specific capacity of ~860 mAh/g, indicating that the metal sulfur battery of the present invention has excellent battery capacity.

[0059] 实施例三 CoS ₅/CNT正极材料的制备（液相合成法） Example 3 Preparation of CoS ₅ /CNT Cathode Material (Liquid Phase Synthesis Method)

[0060] 将 22 mg碳纳米管均匀地分散在水溶液中，利用超声辅助均匀分散后再加入含 0.8 mmol硫酸钴的水溶液，搅拌均匀后，再缓慢逐滴加入含 l mm₀l Na ₂S ₄的水溶液；经过充分反应十二小吋后，得到最终产物 CoS ₅/CNT，过渡金属硫化物、碳基材料的质量比约为 1:0.11。 [0060] will 22 Mg carbon nanotubes are uniformly dispersed in an aqueous solution, uniformly dispersed by ultrasound, and then added with an aqueous solution containing 0.8 mmol of cobalt sulfate. After stirring uniformly, an aqueous solution containing 1 mm ₀ l Na ₂ S ₄ is slowly added dropwise; After reacting for twelve hours, the final product CoS ₅ /CNT is obtained, and the mass ratio of the transition metal sulfide to the carbon-based material is about 1:0.11.

[0061] 其中，电极的制备及电池的组装同实施例一，测试区间在 1.7-3.0 V，测试结果见图 7，由图 7可以得出， CoS ₅/CNT电极展现出〜 1.9 V的工作电压和〜 1100 mAh/g 的比容量，说明本发明公幵的金属硫电池具备优异的电池容量。 [0061] wherein the preparation of the electrode and the assembly of the battery are the same as in the first embodiment, the test interval is 1.7-3.0 V, and the test result is shown in FIG. 7. It can be concluded from FIG. 7 that the CoS ₅ /CNT electrode exhibits a work of ~1.9 V. The voltage and the specific capacity of ~1100 mAh/g indicate that the metal sulfur battery of the present invention has excellent battery capacity.

[0062] 图 8为实施例一、二、三中不含炭基材料条件下所合成的 MoS ₃、 TiS ₄、 CoS ₅ 的 XRD图谱；由图可知用本发明合成的富硫过渡金属硫化物是一类非晶或近非晶状态的材料。 8 is an XRD pattern of MoS ₃ , TiS ₄ , CoS ₅ synthesized in the absence of a carbon-based material in Examples 1, 2, and 3; FIG. 8 is a view showing the sulfur-rich transition metal sulfide synthesized by the present invention. It is a type of material that is amorphous or nearly amorphous.

[0063] 实施例四过渡金属铜辅助的锂硫电池 [0063] Embodiment 4 Transition metal copper assisted lithium sulfur battery

[0064] 将 50 nm的铜粉、升华硫按 2:1 (摩尔比）混合制成复合型硫正极材料，再将该复合材料与导电炭黑、聚偏氟乙烯（PVDF) 粘结剂按 7:2:1混合在 N-甲基吡咯烷酮（NMP) 中制浆，搅拌 10小吋使浆液充分混合均匀后将浆液在铜箔上涂膜，后在真空烘箱中 60°C烘干 24小吋。 [0064] mixing 50 nm copper powder and sublimed sulfur in a 2:1 (molar ratio) to form a composite sulfur cathode material, and then pressing the composite material with conductive carbon black and polyvinylidene fluoride (PVDF) binder Mix 7:2:1 in N-methylpyrrolidone (NMP), stir for 10 hours, mix the slurry thoroughly, then coat the slurry on copper foil, then dry in a vacuum oven at 60 °C for 24 hours. Inches.

[0065] 电池组装过程与传统金属-硫电池相同，电池型号为 CR2032, 隔膜采用双层隔膜结构，一层为玻璃纤维隔膜，直径为 1.6 mm，置于正极一侧；一层为聚丙烯隔膜，直径为 1.9 mm，置于金属锂负极一侧。电解液选用醚类电解液，溶质为双三氟甲烷磺酰亚胺锂（LiTFSI) ；溶剂为 1,3-二氧环戊烷和乙二醇二甲醚（D OL/DME) 按体积比 1:1的混合液；溶质浓度为 1 M。 [0065] The battery assembly process is the same as that of the conventional metal-sulfur battery, the battery type is CR2032, the diaphragm adopts a double-layer diaphragm structure, one layer is a glass fiber diaphragm, the diameter is 1.6 mm, and is placed on the positive electrode side; , 1.9 mm in diameter, placed on the negative side of the metal lithium. The electrolyte is selected from an ether electrolyte, and the solute is lithium bis(trifluoromethanesulfonimide) (LiTFSI); the solvent is 1,3-dioxocyclopentane and ethylene glycol dimethyl ether (D OL/DME) by volume ratio a 1:1 mixture; the solute concentration is 1 M.

[0066] 附图 9为该电池在充电速率为 0.5 A/g _s (相对于 S计算）；放电速率为 1.5 A/g _s ( 相对于 S计算）下的循环曲线。该电池中硫的负载量为 l mg/cm 2。结合图 1，按本方法制备的过渡金属铜辅助的锂硫电池的放电平台为 1.7 V，充电主平台为 1.8 V。在硫的负载量为 l mg/cm 2的情况下，电池容量维持在 950 mAh/g _s左右，持续工作 1000个循环，并且充放电效率平均为 99.3%，由此证明通过过渡金属铜的辅助有效地抑制了多硫化锂溶出导致的穿梭效应。 9 is a cycle curve of the battery at a charging rate of 0.5 A/g _s (calculated relative to S) and a discharge rate of 1.5 A/g _s (calculated relative to S). The amount of sulfur supported in the battery was 1 mg/cm 2 . Referring to Figure 1, the transition metal copper-assisted lithium-sulfur battery prepared according to the method has a discharge platform of 1.7 V and a charging main platform of 1.8 V. When the sulfur loading is 1 mg/cm 2 , the battery capacity is maintained at around 950 mAh/g _s , and the operation continues for 1000 cycles, and the charge and discharge efficiency is 99.3% on average, thus demonstrating the assistance of transition metal copper. The shuttle effect caused by the dissolution of lithium polysulfide is effectively suppressed.

[0067] 实施例五过渡金属钒辅助的锂硫电池 Example 5 Transition Metal Vanadium-Assisted Lithium-Sulfur Battery

[0068] 将金属钒粉末、升华硫按 2:1 (摩尔比）混合制成复合型硫正极材料，再将该复合材料与导电炭黑、聚偏氟乙烯（PVDF) 粘结剂按 7:2:1混合在 N-甲基吡咯烷酮（NMP) 中制浆，搅拌 10小吋使浆液充分混合均匀后将浆液在铜箔上涂膜，后在真空烘箱中 60°C烘干 24小吋。 [0068] mixing metal vanadium powder and sublimed sulfur in a ratio of 2:1 (molar ratio) to form a composite sulfur cathode material, and then The composite material is mixed with conductive carbon black and polyvinylidene fluoride (PVDF) binder in N:methylpyrrolidone (NMP) at a ratio of 7:2:1. After stirring for 10 hours, the slurry is thoroughly mixed and the slurry is placed. The film was coated on copper foil and dried in a vacuum oven at 60 ° C for 24 hours.

[0069] 电池组装过程与传统金属-硫电池相同，电池型号为 CR2032, 隔膜为玻璃纤维隔膜；电解液选用酯类电解液，溶质为六氟磷酸锂（LiPF6) ；溶剂为碳酸乙烯酯和碳酸二乙酯（EC/DEC) 按体积比 1:1的混合液；溶质浓度为 1 M。 [0069] The battery assembly process is the same as the traditional metal-sulfur battery, the battery type is CR2032, the diaphragm is a glass fiber diaphragm; the electrolyte is an ester electrolyte, the solute is lithium hexafluorophosphate (LiPF6); the solvent is ethylene carbonate and diethyl carbonate. (EC/DEC) A mixture of 1:1 by volume; solute concentration of 1 M.

[0070] 附图 10为该电池在充放电速率为 l A/g _s (相对于 S计算）下的循环曲线，所设充放电电流为 2 mA。该电池中硫的负载量为 1 mg/cm 2。结合图 10，按本方法制备的过渡金属钒辅助的锂硫电池在电压区间为 0.1V-3V, 硫的负载量为 0.7 mg/cm 2，充放电速率为 0.5 A/g _s的情况下，电池容量维持在 750 mAh/g _s左右，持续工作 130个循环，并且充放电效率平均为 99.3%，由此证明通过过渡金属钒的辅助锂硫电池未出现穿梭效应。 10 is a cycle curve of the battery at a charge and discharge rate of 1 A/g _s (calculated with respect to S), and the charge and discharge current is set to 2 mA. The amount of sulfur supported in the battery was 1 mg/cm 2 . Referring to FIG. 10, the transition metal vanadium-assisted lithium-sulfur battery prepared by the method has a voltage range of 0.1V-3V, a sulfur loading of 0.7 mg/cm 2 , and a charge and discharge rate of 0.5 A/g _s . The battery capacity was maintained at around 750 mAh/g _s , and it continued to operate for 130 cycles, and the charge and discharge efficiency averaged 99.3%, thus demonstrating that there is no shuttle effect in the auxiliary lithium-sulfur battery through the transition metal vanadium.

[0071] 实施例六过渡金属钼辅助的钠硫电池 Example 6 Transition Metal Molybdenum Assisted Sodium Sulfur Battery

[0072] 将金属钼粉末、升华硫按 2:1 (摩尔比）混合制成复合型硫正极材料，再将该复合材料与导电炭黑、聚偏氟乙烯（PVDF) 粘结剂按 7:2:1混合在 N-甲基吡咯烷酮（NMP) 中制浆，搅拌 10小吋使浆液充分混合均匀后将浆液在铜箔上涂膜，后在真空烘箱中 60°C烘干 24小吋。 [0072] The metal molybdenum powder and the sublimed sulfur are mixed in a ratio of 2:1 (molar ratio) to form a composite sulfur cathode material, and then the composite material and the conductive carbon black and polyvinylidene fluoride (PVDF) binder are 7: 2:1 was mixed and slurried in N-methylpyrrolidone (NMP). After stirring for 10 hours, the slurry was thoroughly mixed, and the slurry was coated on a copper foil, and then dried in a vacuum oven at 60 ° C for 24 hours.

[0073] 电池组装过程与传统金属-硫电池相同，电池型号为 CR2032, 隔膜为聚丙烯隔膜；电解液选用酯类电解液，溶质为高氯酸钠（NaC10 ₄) ；碳酸乙烯酯和碳酸二乙酯（EC/DEC) 按体积比 1:1的混合液；溶质浓度为 1 M。 [0073] The battery assembly process is the same as the traditional metal-sulfur battery, the battery type is CR2032, the diaphragm is a polypropylene diaphragm; the electrolyte is selected from an ester electrolyte, the solute is sodium perchlorate (NaC10 ₄ ); the ethylene carbonate and the carbonic acid Ethyl ester (EC/DEC) A mixture of 1:1 by volume; solute concentration of 1 M.

[0074] 附图 11为该电池在充放电速率为 0.1 A/gS (相对于 S计算）下的循环曲线，所设充放电电流为 0.2 mA。该电池中硫的负载量为 1 mg/cm 2。结合图 11，按本方法制备的过渡金属钼辅助的钠硫电池在硫的负载量为 1 mg/cm 2 , 充放电速率为 0.5 A/gs的情况下，该体系经过 10个循环左右的活化过程，电池容量可达到 400 mAh/gs，持续工作 100个循环后衰减至 320mAh/gs，并且充放电效率平均为 99.5% ，由此证明通过过渡金属铜的辅助有效的抑制多硫化钠溶出导致的严重的穿梭效应。 11 is a cycle diagram of the battery at a charge and discharge rate of 0.1 A/gS (calculated with respect to S), and the charge and discharge current is set to 0.2 mA. The amount of sulfur supported in the battery was 1 mg/cm 2 . Referring to Figure 11, the transition metal molybdenum-assisted sodium-sulfur battery prepared according to the method has a sulfur loading of 1 mg/cm 2 and a charge-discharge rate of 0.5 A/gs, and the system is activated by about 10 cycles. The process, the battery capacity can reach 400 mAh / gs, attenuate to 320 mAh / gs after 100 cycles of continuous operation, and the charge and discharge efficiency is 99.5% on average, which proves that the assisted effective inhibition of sodium polysulfide dissolution by the transition metal copper A severe shuttle effect.

[0075] 实施例七过渡金属镍辅助的锂硫电池 [0076] 0.32 M Li ₂S ₈ (浓度按 S计算）正极电解液的制备：在手套箱中，取 10 mL 含有 1摩尔双三氟甲烷磺酰亚胺锂（LiTFSI) 的 1,3-二氧环戊烷和乙二醇二甲醚 (DOL/DME) (体积比 1:1) 的醚类电解液于带盖 20 mL玻璃瓶中待用。用天平称取 18.4 mg硫化锂加入电解液中并同吋幵始搅拌，使硫化锂在搅拌吋呈现悬浊液状态。接着称取升华硫（99.9 %) 89.8 mg, 少量多次加入含有硫化锂的电解液中，在加热板上加热到 80°C，全程搅拌，高温反应 5小吋，后降至室温，搅拌 1 2小吋，再升温至 80°C保持 3小吋，后降温（若降温后仍有沉淀，则适当重复上述过程），最终形成棕红色溶液。 Example 7 Transition Metal Nickel Assisted Lithium Sulfur Battery [0076] 0.32 M Li ₂ S ₈ (concentration calculated as S) Preparation of positive electrode electrolyte: In a glove box, 10 mL of 1,3-two containing 1 mol of lithium bistrifluoromethanesulfonimide (LiTFSI) was taken. Oxygen cyclopentane and ethylene glycol dimethyl ether (DOL/DME) (1:1 by volume) ether electrolyte were used in a 20 mL glass vial with lid. Weigh 18.4 mg of lithium sulphide into the electrolyte with a balance and start stirring at the same time, so that the lithium sulphide is in a suspension state after stirring. Then weighed sublimed sulfur (99.9 %) 89.8 mg, added a small amount to the electrolyte containing lithium sulfide multiple times, heated to 80 ° C on a hot plate, stirred all the way, reacted at high temperature for 5 hours, then cooled to room temperature, stirring 1 2 small sputum, and then warmed to 80 ° C for 3 hours, and then cooled (if there is still precipitation after cooling, the above process is repeated), finally forming a reddish brown solution.

[0077] 选用密度为 250 g/cm ²、厚度为 1.6 mm、孔隙为 90 ppm、纯度为 99.9 <¾的泡沫镍，切割成直径 1.6 cm的圆片以做正极集流体用。 [0077] A foamed nickel having a density of 250 g/cm ² , a thickness of 1.6 mm, a porosity of 90 ppm, and a purity of 99.9 <3⁄4 was used, and was cut into a disk having a diameter of 1.6 cm for use as a positive electrode current collector.

[0078] 在手套箱中，将泡沫镍集流体置于电池正极壳中（电池型号为 CR2032) ，取上述正极液 200 μί，逐滴滴加在泡沫镍上，直到泡沫镍不能容纳更多正极液，将直径为 1.6 mm的玻璃纤维隔膜置于集流体上方，将剩余正极液滴加在的玻璃纤维隔膜上，此吋若隔膜未被完全润湿则补加空白醚类电解液（不含多硫化锂），之后依次将聚丙烯隔膜（直径 1.9 mm) 、金属锂片、不锈钢片、弹簧片、负极电池壳按顺序摆放，压制电池。 [0078] In the glove box, the foamed nickel current collector is placed in the battery positive electrode case (battery model CR2032), and the above positive electrode liquid is taken 200 μί, and added dropwise on the foamed nickel until the foamed nickel cannot accommodate more positive electrodes. Liquid, a 1.6 mm diameter glass fiber membrane is placed over the current collector, and the remaining positive electrode droplets are applied to the glass fiber membrane. If the membrane is not completely wetted, a blank ether electrolyte is added. Lithium polysulfide), followed by placing the polypropylene diaphragm (diameter 1.9 mm), lithium metal sheet, stainless steel sheet, spring piece, and negative battery case in order to press the battery.

[0079] 附图 12为该电池在充放电速率为 1 A/g s下的循环曲线，所设充放电电流为 2 mA。结合图 12，按本方法制备的过渡金属镍辅助的锂硫电池，刚幵始几个循环表现出锂硫电池的充放电行为，随着循环的进行，镍逐渐参与到充放电过程中，造成了压降行为，电压平台稳定后为 1.4 V。在硫的负载量为 l mg/cm 2，充放电速率为 1 A/g _s的情况下，该体系能持续工作 250个循环，电池容量维持在 600 mAh/g _s左右，并且在电池稳定后充放电效率高达 99.8%，由此证明通过过渡金属镍的辅助抑制了多硫化锂溶出导致的穿梭效应。 12 is a cycle diagram of the battery at a charge and discharge rate of 1 A/gs, and the charge and discharge current is set to 2 mA. Referring to FIG. 12, the transition metal nickel-assisted lithium-sulfur battery prepared according to the method exhibits the charge and discharge behavior of the lithium-sulfur battery in a few cycles, and as the cycle progresses, nickel gradually participates in the charging and discharging process, resulting in The voltage drop behavior is 1.4 V after the voltage platform is stable. When the sulfur loading is 1 mg/cm 2 and the charge and discharge rate is 1 A/g _s , the system can work continuously for 250 cycles, the battery capacity is maintained at about 600 mAh/g _s , and after the battery is stabilized. The charge and discharge efficiency is as high as 99.8%, which proves that the shuttle effect caused by the dissolution of lithium polysulfide is suppressed by the aid of the transition metal nickel.

[0080] 实施例八过渡金属铜辅助的高负载锂硫电池 Embodiment 8 Transition metal copper assisted high load lithium sulfur battery

[0081] 2 M Li ₂S ₈ (浓度按 S计算）正极液的制备：在手套箱中，取 10 mL含有 1摩尔双三氟甲烷磺酰亚胺锂（LiTFSI) 的 1,3-二氧环戊烷和乙二醇二甲醚（DOL/DM E) (体积比 1:1) 的醚类电解液于带盖 20 mL玻璃瓶中待用。用天平称取 114.7 mg硫化锂加入电解液中并同吋幵始搅拌，使硫化锂在搅拌吋呈现悬浊液状态。接着称取升华硫（99.9 %) 560 mg，少量多次加入含有硫化锂的电解液中，在加热板上加热到 80°C，全程搅拌，高温反应 10小吋，后降至室温，搅拌 12小吋，再升温至 80°C保持 3小吋，后降温（若降温后仍有沉淀，则适当重复上述过程），最终形成棕红色溶液。 2 M Li ₂ S ₈ (concentration calculated as S) Preparation of the positive electrode solution: In a glove box, 10 mL of 1,3-dioxe containing 1 mol of lithium bistrifluoromethanesulfonimide (LiTFSI) was taken. An ether electrolyte of cyclopentane and ethylene glycol dimethyl ether (DOL/DM E) (1:1 by volume) was used in a 20 mL glass vial with a lid. Weigh 114.7 mg of lithium sulphide into the electrolyte with a balance and start stirring at the same time, so that the lithium sulphide is in a suspension state after stirring. Then weighed sublimed sulfur (99.9 %) 560 mg, added a small amount to the electrolyte containing lithium sulfide multiple times, heated to 80 ° C on a hot plate, stirred for the whole process, reacted at high temperature for 10 hours, then cooled to room temperature, stirred 12 After the small temperature, the temperature is raised to 80 ° C for 3 hours, and then the temperature is lowered (if there is still precipitation after cooling, the above process is appropriately repeated), and finally a brown-red solution is formed.

[0082] 选用密度为 500 g/cm ²、厚度为 1.6 mm、孔隙为 90 ppm、纯度为 99.9 <¾的泡沫铜[0082] Foam copper having a density of 500 g/cm ² , a thickness of 1.6 mm, a porosity of 90 ppm, and a purity of 99.9 <3⁄4 is selected.

。组装电池前用压片机将泡沫铜厚度压至 0.5 mm左右，之后切割成直径 1.6 cm的圆片以做正极集流体用。 . Before assembling the battery, the thickness of the foamed copper was pressed to about 0.5 mm by a tableting machine, and then cut into a disk having a diameter of 1.6 cm to serve as a positive electrode current collector.

[0083] 在手套箱中，将泡沫铜集流体置于电池正极壳中（电池型号为 CR2032) ，取上述正极液 50 μί，逐滴滴加在泡沫铜上，将直径为 1.6 mm的玻璃纤维隔膜置于集流体上方，用空白醚类电解液（不含多硫化锂）润湿隔膜，之后依次将聚丙烯隔膜（直径 1.9 mm) 、金属锂片、不锈钢片、弹簧片、负极电池壳按顺序摆放，压制电池。 [0083] In the glove box, the foamed copper current collector was placed in the battery positive electrode case (battery model CR2032), and the above positive electrode liquid was taken 50 μί, and added dropwise to the foamed copper to make a fiberglass having a diameter of 1.6 mm. The diaphragm is placed above the current collector, and the separator is wetted with a blank ether electrolyte (excluding lithium polysulfide), followed by a polypropylene diaphragm (1.9 mm in diameter), a lithium metal sheet, a stainless steel sheet, a spring piece, and a negative battery case. Place them in sequence and press the battery.

[0084] 附图 13为过渡金属铜辅助的锂硫电池在放电速率为 0.3 A/g s , 充电速率为 0.1 A/g _s下的充放电曲线，所设放电电流为 1.92 mA，充电电流为 0.64 mA。测试前将电池搁置 2小吋，使部分多硫化锂先和泡沫铜反应生成一定量的硫化亚铜。由图 13可见，按本方法制备锂硫电池，在硫的负载量达到 3.2 mg/cm 2吋，该体系仍然能持续工作 400圈，电池经不断活化，容量可从 800 mAh/g _s增长到 1200 mAh/g s，由此可见通过过渡金属铜的辅助可以解决锂硫电池中负载量难以提高的问题。并且充放电效率平均为 99.5%，由此证明通过过渡金属的辅助有效地抑制了多硫化锂溶出导致的穿梭效应，并提高了电池的循环寿命。 13 is a charge-discharge curve of a transition metal copper-assisted lithium-sulfur battery at a discharge rate of 0.3 A/gs and a charge rate of 0.1 A/g _s , with a discharge current of 1.92 mA and a charging current of 0.64. mA. The battery was left for 2 hours before the test, and a portion of the lithium polysulfide was first reacted with the foamed copper to form a certain amount of cuprous sulfide. It can be seen from Fig. 13 that the lithium-sulfur battery is prepared according to the method. When the sulfur loading reaches 3.2 mg/cm 2 , the system can still work for 400 cycles, and the battery is continuously activated, and the capacity can be increased from 800 mAh/g _s to 1200 mAh/gs, it can be seen that the help of the transition metal copper can solve the problem that the load in the lithium-sulfur battery is difficult to increase. Moreover, the charge and discharge efficiency averages 99.5%, which proves that the shuttle effect caused by the dissolution of lithium polysulfide is effectively suppressed by the aid of the transition metal, and the cycle life of the battery is improved.

[0085] 实施例九过渡金属铜辅助的钠硫电池 Example 9 Transition Metal Copper Assisted Sodium Sulfur Battery

[0086] l M Na ₂S ₆ (浓度按 S计算）正极液的制备：在手套箱中，取 10 mL含有 1摩尔三氟甲基磺酸钠（NaS0 ₃CF ₃) 的二乙二醇二甲醚（DGME) 的醚类电解液于带盖 20 mL玻璃瓶中待用。用天平称取 130 mg硫化钠加入电解液中并同吋幵始搅拌，使硫化锂在搅拌吋呈现悬浊液状态。接着称取升华硫（99.9 %) 266.7 mg, 少量多次加入含有硫化钠的电解液中，在加热板上加热到 80°C，全程搅拌，高温反应 10小吋最终形成棕红色溶液。 l M Na ₂ S ₆ (concentration calculated as S) Preparation of the catholyte: In a glove box, 10 mL of diethylene glycol II containing 1 mol of sodium trifluoromethanesulfonate (NaS0 ₃ CF ₃ ) was taken. The ether electrolyte of methyl ether (DGME) was used in a 20 mL glass bottle with a lid. Weigh 130 mg of sodium sulfide into the electrolyte with a balance and start stirring at the same time to make the lithium sulfide exhibit a suspension state after stirring. Then weighed sublimed sulfur (99.9 %) 266.7 mg, added a small amount to the electrolyte containing sodium sulfide multiple times, heated to 80 ° C on a hot plate, stirred for the whole process, and reacted at high temperature for 10 hours to finally form a brown-red solution.

[0087] 选用密度为 250 g/cm ²、厚度为 1.6 mm、孔隙为 90 ppm、纯度为 99.9 <¾的泡沫铜，切割成直径 1.6 cm的圆片以做正极集流体用。 [0087] Foam copper having a density of 250 g/cm ² , a thickness of 1.6 mm, a porosity of 90 ppm, and a purity of 99.9 <3⁄4 is selected. , cut into a 1.6 cm diameter disc for use as a positive current collector.

[0088] 在手套箱中，将泡沫铜集流体置于电池正极壳中（电池型号为 CR2032) ，取上述正极液 64 μί，硫负载量为 lmg/cm ²，逐滴滴加在泡沫铜上，直到泡沫铜不能容纳更多正极液，将直径为 1.6 mm的玻璃纤维隔膜置于集流体上方，将剩余正极液滴加在的玻璃纤维隔膜上，此吋若隔膜未被完全润湿则补加空白醚类电解液（不含多硫化钠），之后依次将聚丙烯隔膜（直径 1.9 mm) 、金属钠片、不锈钢片、弹簧片、负极电池壳按顺序摆放，压制电池。 [0088] In the glove box, the foamed copper current collector is placed in the battery positive electrode case (battery model CR2032), taking the above positive electrode liquid 64 μί, sulfur loading is 1 mg/cm ² , and dropping on the foam copper Until the foamed copper cannot accommodate more catholyte, place a 1.6 mm diameter glass fiber membrane over the current collector and add the remaining positive electrode droplets to the glass fiber membrane. If the membrane is not completely wetted, A blank ether electrolyte (excluding sodium polysulfide) was added, and then a polypropylene separator (diameter: 1.9 mm), a metal sodium plate, a stainless steel sheet, a spring piece, and a negative battery case were sequentially placed, and the battery was pressed.

[0089] 附图 14为过渡金属硫辅助的钠硫电池在充放电速率为 0.5 A/g _s的循环曲线，所设充放电电流为 l mA。测试前将电池在 0.1 A/g ₅的速率下预循环 5圈。结合图 14 ，按本方法制备的钠硫电池，在硫的负载量为 l mg/cm ²，充放电速率为 0.5 A/g _s 的情况下，该体系能持续工作 175个循环，电池经不断活化，容量可从 350 mAh/g _s增长到 450 mAh/g _s。并且充放电效率平均为 98.8<¾，由此证明通过过渡金属铜的辅助可以有效的抑制多硫化钠溶出导致的严重的穿梭效应，使电池的循环寿命大大提高。 14 is a cycle curve of a transition metal sulfur-assisted sodium-sulfur battery at a charge and discharge rate of 0.5 A/g _s , and a charge and discharge current of 1 mA is set. The battery was pre-circulated 5 turns at a rate of 0.1 A/g ₅ before testing. Referring to Figure 14, the sodium-sulfur battery prepared according to the method has a sulfur loading of 1 mg/cm ² and a charge-discharge rate of 0.5 A/g _s , and the system can continue to work for 175 cycles. With activation, the capacity can be increased from 350 mAh/g _s to 450 mAh/g _s . Moreover, the charge and discharge efficiency averages 98.8<3⁄4, which proves that the secondary shuttle effect caused by the dissolution of sodium polysulfide can be effectively suppressed by the aid of the transition metal copper, and the cycle life of the battery is greatly improved.

[0090] 对比例一 Comparative Example 1

[0091] 将实施例七将泡沫镍集流体换为亲水碳纸测试电池性能；电池的组装过程与实施例七相同。 The battery performance was tested by changing the foamed nickel current collector to hydrophilic carbon paper in Example 7; the assembly process of the battery was the same as in the seventh embodiment.

[0092] 电池组装完成后直接测试，设置充放电电流为 0.2 mA，对应的充放电速率为 0.1 A/g _s。附图 15为没有过渡金属辅助下的锂硫电池。对比图 12和图 15，该电池起始容量很低，只有 300 mAh/g _s左右，并且随着循环的进行容量还在不断衰减，并伴随着及其严重的穿梭效应，库伦效率低于 80%，由此可见，在本发明的电池体系中泡沫铜集流体是必不可少的。将循环 100圈后的该电池和实施例七中的过渡金属镍辅助的锂硫电池拆幵，观察电池内部情况。图 16为二者对比图，由此可见，经过 100圈循环，本发明中的锂硫电池隔膜为白色，说明电解液中没有多余的多硫化锂；该对比例中的电池隔膜为黄色，说明正极液中的多硫化锂未被完全应用，结合图 15可知该对比例中严重的穿梭效应是由这些多硫化锂造成。 [0092] After the battery assembly is completed, the direct test is performed, and the charging and discharging current is set to 0.2 mA, and the corresponding charging and discharging rate is 0.1 A/g _s . Figure 15 is a lithium sulfur battery without the aid of a transition metal. Comparing Figure 12 with Figure 15, the initial capacity of the battery is very low, only about 300 mAh / g _s , and the capacity is still attenuating as the cycle progresses, accompanied by its severe shuttle effect, the Coulomb efficiency is lower than 80 Thus, it can be seen that a foamed copper current collector is indispensable in the battery system of the present invention. The battery after the cycle of 100 cycles and the transition metal nickel-assisted lithium-sulfur battery in the seventh embodiment were taken apart, and the inside of the battery was observed. Figure 16 is a comparison of the two, it can be seen that after 100 cycles, the lithium-sulfur battery separator of the present invention is white, indicating that there is no excess lithium polysulfide in the electrolyte; the battery separator in the comparative example is yellow, indicating The lithium polysulfide in the positive electrode liquid was not completely used. It can be seen from Fig. 15 that the severe shuttle effect in the comparative example was caused by these lithium polysulfides.

Claims

权利要求书 Claim

一种金属-硫电池，其特征在于，所述金属 -硫电池包括正极、负极以及电解液；所述负极为金属；所述正极包括过渡金属硫化物；或者所述正极包括含硫材料以及过渡金属材料；所述电解液包括液态电解液和固态电解液。 A metal-sulfur battery, characterized in that the metal-sulfur battery comprises a positive electrode, a negative electrode and an electrolyte; the negative electrode is a metal; the positive electrode comprises a transition metal sulfide; or the positive electrode comprises a sulfur-containing material and a transition a metal material; the electrolyte includes a liquid electrolyte and a solid electrolyte.

根据权利要求 1所述金属-硫电池，其特征在于，所述过渡金属硫化物的化学式为 MS _x，其中 x≥3; 所述负极金属包括锂、钠、钾、镁、铝；所述过渡金属包括钛、钒、铁、钴、镍、铜、锌、钼、钨；所述含硫材料为硫单质、负极金属硫化物或者负极金属多硫化物；所述过渡金属材料为单一过渡金属材料或 /和过渡金属合金材料。 The metal-sulfur battery according to claim 1, wherein said transition metal sulfide has a chemical formula of MS _x , wherein _x ≥ 3; said negative electrode metal comprises lithium, sodium, potassium, magnesium, aluminum; The metal includes titanium, vanadium, iron, cobalt, nickel, copper, zinc, molybdenum, tungsten; the sulfur-containing material is sulfur elemental, negative metal sulfide or negative metal polysulfide; the transition metal material is a single transition metal material Or / and transition metal alloy materials.

根据权利要求 1所述金属-硫电池，其特征在于，所述包括过渡金属硫化物的正极还可包括碳基材料；所述过渡金属硫化物、碳基材料的质量比为 1: (0〜2) ；所述碳基材料包括碳黑、碳纳米管、石墨烯、碳纤维或者多孔碳。 The metal-sulfur battery according to claim 1, wherein the positive electrode including the transition metal sulfide further comprises a carbon-based material; and the mass ratio of the transition metal sulfide to the carbon-based material is 1: (0~) 2); The carbon-based material includes carbon black, carbon nanotubes, graphene, carbon fiber or porous carbon.

根据权利要求 1所述金属-硫电池，其特征在于，所述过渡金属材料为粉末、纤维、薄膜、泡沫或者三维多孔结构；所述粉末为微米颗粒、纳米颗粒、纳米线、二维层状纳米片中的一种或几种。 The metal-sulfur battery according to claim 1, wherein the transition metal material is a powder, a fiber, a film, a foam or a three-dimensional porous structure; the powder is a microparticle, a nanoparticle, a nanowire, a two-dimensional layer One or several of the nanosheets.

一种金属-硫电池的制备方法，其特征在于，包括以下步骤，在碳基材料存在下，或者不在碳基材料存在下，以过渡金属前驱体化合物为原料，制备碳基材料与过渡金属硫化物复合体系或者过渡金属硫化物A method for preparing a metal-sulfur battery, comprising the steps of: preparing a carbon-based material and transition metal sulfide in the presence of a carbon-based material or in the presence of a carbon-based material using a transition metal precursor compound as a raw material Compound system or transition metal sulfide

；然后将所述碳基材料与过渡金属硫化物复合体系或者过渡金属硫化物制备为正极；以金属为负极；然后将所述正极、负极、电解液组装制备金属-硫电池。 Then, the carbon-based material and the transition metal sulfide composite system or the transition metal sulfide are prepared as a positive electrode; the metal is used as a negative electrode; and then the positive electrode, the negative electrode, and the electrolyte are assembled to prepare a metal-sulfur battery.

一种金属-硫电池的制备方法，其特征在于，将过渡金属材料与含硫材料组合制备正极，再与负极、电解液组装制备金属-硫电池；或者将可溶性含硫材料溶于液体电解液后，再与过渡金属材料组合制备正极，再与负极组装制备金属-硫电池。 A method for preparing a metal-sulfur battery, characterized in that a transition metal material is combined with a sulfur-containing material to prepare a positive electrode, and then a metal-sulfur battery is assembled by assembling the negative electrode and the electrolyte; or the soluble sulfur-containing material is dissolved in the liquid electrolyte. Thereafter, a positive electrode is prepared in combination with a transition metal material, and then assembled with a negative electrode to prepare a metal-sulfur battery.

根据权利要求 5或者 6所述金属-硫电池的制备方法，其特征在于，所述负极包括锂、钠、钾、镁、铝；所述过渡金属包括钛、钒、铁、钴、镍、铜、锌、钼、钨；所述碳基材料包括碳黑、碳纳米管、石墨烯、碳纤维或者多孔碳；所述电解液包括液态电解液和固态电解液；利用酸性水解法、液相合成法、固相球磨法、溶剂热法或者热分解法制备碳基材料与过渡金属硫化物复合体系或者过渡金属硫化物；在碳基材料存在下，首先将碳基材料与过渡金属前驱体化合物混合，再制备碳基材料与过渡金属硫化物复合体系；所述碳基材料与过渡金属硫化物复合体系的粒径为 1〜10000纳米；所述过渡金属硫化物的粒径为 1 〜10000纳米；所述含硫材料为硫单质、负极金属硫化物或者负极金属多硫化物，所述过渡金属材料为粉末、纤维、薄膜、泡沫或者三维多孔结构。 A method of preparing a metal-sulfur battery according to claim 5 or 6, wherein The negative electrode includes lithium, sodium, potassium, magnesium, aluminum; the transition metal includes titanium, vanadium, iron, cobalt, nickel, copper, zinc, molybdenum, tungsten; the carbon-based material includes carbon black, carbon nanotubes, graphite a olefin, a carbon fiber or a porous carbon; the electrolyte comprises a liquid electrolyte and a solid electrolyte; and the carbon-based material and the transition metal sulfide are prepared by an acidic hydrolysis method, a liquid phase synthesis method, a solid phase ball milling method, a solvothermal method or a thermal decomposition method; Composite system or transition metal sulfide; in the presence of a carbon-based material, first mixing a carbon-based material with a transition metal precursor compound, and then preparing a carbon-based material and a transition metal sulfide composite system; the carbon-based material and transition metal The sulfide composite system has a particle diameter of 1 to 10000 nm; the transition metal sulfide has a particle diameter of 1 to 10000 nm; and the sulfur-containing material is sulfur elemental, negative metal sulfide or negative metal polysulfide, The transition metal material is a powder, a fiber, a film, a foam or a three-dimensional porous structure.

[权利要求 8] 根据权利要求 7所述金属-硫电池的制备方法，其特征在于，在碳基材料存在下，酸性水解法为，将碳基材料分散在水溶液中，再加入过渡金属前驱物，搅拌均匀后，再逐滴加入酸溶液，反应后，得到碳基材料与过渡金属硫化物复合体系；固相球磨法为，将碳基材料、过渡金属和硫粉按计量比混合均匀，转移到球磨罐中抽真空，再于惰性气体下装配好后，转移至球磨机球磨得到碳基材料与过渡金属硫化物复合体系；液相合成法为将碳基材料均匀地分散在水溶液中，再加入过渡金属前驱物，搅拌均匀后，再逐滴加入活泼金属多硫化物溶液，反应得到碳基材料与过渡金属硫化物复合体系；不在碳基材料存在下，酸性水解法为，向过渡金属前驱物中逐滴加入酸溶液，反应后，得到过渡金属硫化物；固相球磨法为，将过渡金属和硫粉按计量比混合均匀，转移到球磨罐中抽真空，再于惰性气体下装配好后，转移至球磨机球磨得到过渡金属硫化物；液相合成法为将向过渡金属前驱物中逐滴加入活泼金属多硫化物溶液，反应得到过渡金属硫化物；所述粉末为微米颗粒、纳米颗粒、纳米线、二维层状纳米片中的一种或几种。 [Claim 8] The method for producing a metal-sulfur battery according to claim 7, wherein in the presence of a carbon-based material, the acidic hydrolysis method is: dispersing a carbon-based material in an aqueous solution, and then adding a transition metal precursor After stirring evenly, the acid solution is added dropwise, and after the reaction, a carbon-based material and a transition metal sulfide composite system are obtained; the solid phase ball milling method is to uniformly mix the carbon-based material, the transition metal and the sulfur powder by a metering ratio, and transfer After vacuuming in a ball mill tank, and then assembling it under inert gas, transferring to a ball mill to obtain a carbon-based material and a transition metal sulfide composite system; liquid phase synthesis method is to uniformly disperse the carbon-based material in an aqueous solution, and then add The transition metal precursor is stirred evenly, and then the active metal polysulfide solution is added dropwise to obtain a composite system of the carbon-based material and the transition metal sulfide; in the absence of the carbon-based material, the acidic hydrolysis method is a transition metal precursor The acid solution is added dropwise, and after the reaction, a transition metal sulfide is obtained; the solid phase ball milling method is The metal and sulfur powder are uniformly mixed according to the metering ratio, transferred to a ball mill tank for vacuuming, and then assembled under inert gas, transferred to a ball mill for ball milling to obtain a transition metal sulfide; liquid phase synthesis method is to be a transition metal precursor The active metal polysulfide solution is added dropwise to obtain a transition metal sulfide; the powder is one or more of microparticles, nanoparticles, nanowires, and two-dimensional layered nanosheets.

[权利要求 9] 一种金属-硫电池正极材料的制备方法，其特征在于，包括以下步骤 [Claim 9] A method for preparing a metal-sulfur battery positive electrode material, comprising the following steps

，在碳基材料存在下，或者不在碳基材料存在下，以过渡金属前驱体化合物为原料，制备碳基材料与过渡金属硫化物复合体系或者过渡金属硫化物，然后将所述碳基材料与过渡金属硫化物复合体系或者过渡金属硫化物制备为金属 -硫电池正极材料；或者将过渡金属材料与含硫材料组合制备正极；或者将可溶性含硫材料溶于液体电解液后，再与过渡金属材料组合制备正极；所述含硫材料为硫单质、负极金属硫化物或者负极金属多硫化物，所述过渡金属材料为过渡金属材料粉末、纤维、薄膜、泡沫或者三维多孔结构。 , in the presence of a carbon-based material, or in the absence of a carbon-based material, as a transition metal precursor The compound is used as a raw material to prepare a carbon-based material and a transition metal sulfide composite system or a transition metal sulfide, and then the carbon-based material and the transition metal sulfide composite system or the transition metal sulfide are prepared as a metal-sulfur battery cathode material; or Preparing the positive electrode by combining the transition metal material with the sulfur-containing material; or dissolving the soluble sulfur-containing material in the liquid electrolyte, and then preparing the positive electrode in combination with the transition metal material; the sulfur-containing material is sulfur elemental substance, negative electrode metal sulfide or negative electrode metal A polysulfide, the transition metal material being a transition metal material powder, a fiber, a film, a foam or a three-dimensional porous structure.

[权利要求 10] —种金属 -硫电池正极材料，其特征在于，所述金属-硫电池正极材料由过渡金属硫化物或者碳基材料与过渡金属硫化物复合体系制备得到；或者所述正极包括含硫材料以及过渡金属材料；所述含硫材料为硫单质、负极金属硫化物或者负极金属多硫化物；所述过渡金属包括钛、钒、铁、钴、镍、铜、锌、钼、钨。 [Claim 10] A metal-sulfur battery positive electrode material, wherein the metal-sulfur battery positive electrode material is prepared from a transition metal sulfide or a carbon-based material and a transition metal sulfide composite system; or the positive electrode includes a sulfur-containing material and a transition metal material; the sulfur-containing material is a sulfur elemental substance, a negative electrode metal sulfide or a negative electrode metal polysulfide; and the transition metal includes titanium, vanadium, iron, cobalt, nickel, copper, zinc, molybdenum, tungsten .