CN113809317B - Positive electrode material of liquid or semi-liquid metal battery and application thereof - Google Patents
Positive electrode material of liquid or semi-liquid metal battery and application thereof Download PDFInfo
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 48
- 239000007788 liquid Substances 0.000 title claims abstract description 44
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 24
- 238000004146 energy storage Methods 0.000 claims abstract description 28
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 16
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 13
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 13
- 229910052745 lead Inorganic materials 0.000 claims abstract description 11
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 11
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- 239000006261 foam material Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000002001 electrolyte material Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 abstract description 32
- 229910052751 metal Inorganic materials 0.000 abstract description 32
- 239000010406 cathode material Substances 0.000 abstract description 27
- 239000002994 raw material Substances 0.000 abstract description 16
- 229910052725 zinc Inorganic materials 0.000 abstract description 15
- 238000002844 melting Methods 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 12
- 230000008018 melting Effects 0.000 abstract description 10
- 238000007599 discharging Methods 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 59
- 208000028659 discharge Diseases 0.000 description 17
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 14
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000006260 foam Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910001245 Sb alloy Inorganic materials 0.000 description 4
- 239000002140 antimony alloy Substances 0.000 description 4
- CZJCMXPZSYNVLP-UHFFFAOYSA-N antimony zinc Chemical compound [Zn].[Sb] CZJCMXPZSYNVLP-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910001152 Bi alloy Inorganic materials 0.000 description 3
- ONVGHWLOUOITNL-UHFFFAOYSA-N [Zn].[Bi] Chemical compound [Zn].[Bi] ONVGHWLOUOITNL-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/06—Alloys based on lead with tin as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/08—Alloys based on lead with antimony or bismuth as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or bismuth
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
- C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
一种液态或半液态金属电池的Zn基正极材料及应用,属于储能电池的电极材料领域。本发明正极材料为金属Zn或者Zn与Sn、Bi、Sb、Pb、Te中的一种以上单质形成的Zn合金。液态的Zn或者Zn合金具有较高的放电电压,与现有的负极材料具有较高的匹配性,用于液态或半液态金属电池,在保持电池高容量、长寿命、易放大等优异特性的基础上,可有效减小电池充放电过程中的极化,提高电池的放电电压,进而提高电池的能量密度和能量效率。此外,金属Zn具有较低的熔点(419.5℃)、较低的电阻率(5.9×10‑4Ωcm),Zn合金制备工艺简单、成本低廉,将Zn或者Zn合金用作液态或半液态金属电池正极材料时,还可以提高正极材料的导电性,改善电池的倍率性能,减小电池原料成本。
A Zn-based positive electrode material and application for liquid or semi-liquid metal batteries, belonging to the field of electrode materials for energy storage batteries. The cathode material of the present invention is metal Zn or a Zn alloy formed by Zn and one or more simple substances among Sn, Bi, Sb, Pb and Te. Liquid Zn or Zn alloy has a high discharge voltage and is highly compatible with existing negative electrode materials. It is used in liquid or semi-liquid metal batteries while maintaining the excellent characteristics of the battery such as high capacity, long life, and easy amplification. Basically, it can effectively reduce the polarization during battery charging and discharging, increase the battery's discharge voltage, and thereby improve the battery's energy density and energy efficiency. In addition, metal Zn has a low melting point (419.5°C) and low resistivity (5.9× 10-4 Ωcm). The Zn alloy preparation process is simple and low-cost. Zn or Zn alloys can be used as liquid or semi-liquid metal batteries. When used as a positive electrode material, it can also improve the conductivity of the positive electrode material, improve the rate performance of the battery, and reduce the cost of battery raw materials.
Description
技术领域Technical field
本发明属于储能电池的电极材料,具体涉及一种用于液态或半液态金属电池的正极材料,其能够用于解决液态或半液态金属电池工作电压低、能量密度低、原料成本高的问题。The invention belongs to electrode materials for energy storage batteries, and specifically relates to a cathode material for liquid or semi-liquid metal batteries. It can be used to solve the problems of low operating voltage, low energy density and high raw material cost of liquid or semi-liquid metal batteries. .
背景技术Background technique
风能、太阳能等可再生能源具有资源丰富、清洁无污染等优点,其大力开发和利用可以有效缓解资源、能源和环境之间的矛盾。将高比例的可再生能源接入电网,建立高效率、低成本、环境友好的新型能源结构已成为电网发展的必然选择。然而,可再生能源发电(如风能、太阳能等)具有间歇性和波动性的特点,且受气候、温度等环境因素的影响,直接并入电网会对电网造成较大冲击,严重损害电网的安全性和可靠性。Renewable energy sources such as wind energy and solar energy have the advantages of abundant resources, cleanliness and no pollution. Their vigorous development and utilization can effectively alleviate the contradiction between resources, energy and environment. Integrating a high proportion of renewable energy into the power grid and establishing a high-efficiency, low-cost, and environmentally friendly new energy structure has become an inevitable choice for the development of the power grid. However, renewable energy power generation (such as wind energy, solar energy, etc.) has the characteristics of intermittent and fluctuation, and is affected by environmental factors such as climate and temperature. Direct integration into the power grid will have a great impact on the power grid and seriously damage the security of the power grid. performance and reliability.
大规模储能技术可以平抑可再生能源的间歇性和波动性,显著提高可再生能源的并网效率,保证电网的稳定性、可靠性和安全性,成为了建设智能电网、实现能源互联的关键技术。液态金属电池是一种新兴的大规模储能技术,以其成本低廉、循环寿命长、工作稳定性高等优势,备受储能领域关注。液态金属电池的本质是一类高温熔盐电池,在工作温度下,正、负极和熔盐电解质三者自动分层。在充放电过程中电极结构具有高的自愈性,不会因离子反复脱嵌产生电极变形、枝晶生长等电极微观结构退化等问题。此外,电池装配具有可扩展性,易规模放大,可以适配不同规模的电网。这些特性使得液态金属电池受到电化学储能领域的广泛关注,在未来智能电网储能领域具有广阔的应用前景。Large-scale energy storage technology can smooth out the intermittency and volatility of renewable energy, significantly improve the grid connection efficiency of renewable energy, and ensure the stability, reliability and security of the power grid. It has become the key to building smart grids and realizing energy interconnection. technology. Liquid metal batteries are an emerging large-scale energy storage technology that have attracted much attention in the energy storage field due to their advantages such as low cost, long cycle life, and high working stability. The essence of the liquid metal battery is a type of high-temperature molten salt battery. At the operating temperature, the positive and negative electrodes and the molten salt electrolyte are automatically stratified. During the charge and discharge process, the electrode structure has high self-healing properties and will not cause problems such as electrode deformation, dendrite growth and other electrode microstructure degradation due to repeated deintercalation of ions. In addition, battery assembly is scalable, easy to scale up, and can be adapted to power grids of different sizes. These characteristics make liquid metal batteries receive widespread attention in the field of electrochemical energy storage and have broad application prospects in the field of smart grid energy storage in the future.
自2012年美国麻省理工学院Sadoway教授团队提出“全液态金属电池”(LiquidMetal Battery)概念以来,该技术引起全球学界和产业界的广泛关注,许多液态金属电池的研究成果被陆续报道。研究学者们相继开发了Bi、Sb、Te等高性能正极材料,并通过有效的合金化策略,在正极中引入Sn、Pb、Ga等第二组元,实现了降低正极熔点、降低正极在熔盐电解质中的溶解度、提高电池能量密度、倍率性能等效果(Advanced Energy Materials 6(2016)1600483;Energy Storage Materials 14(2018)267–271;Journal of PowerSources 472(2020)228634)。然而,正极中添加的Sn、Pb、Ga等第二组元在电池充放电循环过程中并不会提供容量,仅起到惰性溶剂的作用,这大大降低了电池的能量密度,使得应用Sb基和Bi基正极材料的电池能量密度低于260Wh kg-1(基于正负极材料)。对于Te基正极材料,其高达1.6V的放电电压,使其具有495Wh kg-1的高能量密度,但Te在熔盐电解质中较高的溶解度使得电池存在自放电率较大、库仑效率低、循环稳定性差等诸多不足。基于上述分析,目前已报道的正极材料在能量密度或循环寿命方面,难以满足大规模储能的需求,严重制约了液态或半液态金属电池的发展及应用。因而,开发新型高电压、高能量密度、优良循环性能的正极材料,对于液态或半液态金属电池在储能领域的实际应用,具有十分重要的意义。Since the team of Professor Sadoway of the Massachusetts Institute of Technology proposed the concept of "Liquid Metal Battery" in 2012, the technology has attracted widespread attention from academic and industrial circles around the world, and many research results of liquid metal batteries have been reported one after another. Researchers have successively developed high-performance cathode materials such as Bi, Sb, and Te, and introduced second components such as Sn, Pb, and Ga into the cathode through effective alloying strategies to reduce the melting point of the cathode and the melting temperature of the cathode. Solubility in salt electrolytes, improving battery energy density, rate performance and other effects (Advanced Energy Materials 6(2016)1600483; Energy Storage Materials 14(2018)267–271; Journal of PowerSources 472(2020)228634). However, the second components such as Sn, Pb, and Ga added to the positive electrode do not provide capacity during the battery charge and discharge cycle, but only act as inert solvents, which greatly reduces the energy density of the battery and makes the application of Sb-based The battery energy density of Bi-based cathode materials is lower than 260Wh kg -1 (based on cathode and cathode materials). For Te-based cathode materials, its high discharge voltage of 1.6V gives it a high energy density of 495Wh kg -1 . However, the higher solubility of Te in the molten salt electrolyte causes the battery to have a large self-discharge rate, low Coulombic efficiency, and There are many shortcomings such as poor cycle stability. Based on the above analysis, the currently reported cathode materials are difficult to meet the needs of large-scale energy storage in terms of energy density or cycle life, which seriously restricts the development and application of liquid or semi-liquid metal batteries. Therefore, the development of new cathode materials with high voltage, high energy density, and excellent cycle performance is of great significance for the practical application of liquid or semi-liquid metal batteries in the field of energy storage.
发明内容Contents of the invention
本发明提供了一种用于液态或半液态金属电池的正极材料,将其应用于储能电池后,可以解决现有液态或半液态金属电池工作电压低、能量密度低、原料成本高等问题。The present invention provides a cathode material for liquid or semi-liquid metal batteries. When applied to energy storage batteries, it can solve the problems of low operating voltage, low energy density and high raw material cost of existing liquid or semi-liquid metal batteries.
为实现上述目的,本发明采用如下的技术方案:In order to achieve the above objects, the present invention adopts the following technical solutions:
本发明一方面提供了一种用于液态或半液态金属电池的正极材料,其特征在于:In one aspect, the present invention provides a cathode material for a liquid or semi-liquid metal battery, which is characterized by:
该正极材料为金属Zn,或者Zn与Sn、Bi、Sb、Pb、Te中的一种或多种单质形成的Zn合金。The positive electrode material is metal Zn, or a Zn alloy formed by Zn and one or more elements of Sn, Bi, Sb, Pb, and Te.
进一步地,以上所述正极材料的摩尔百分比为:Zn2-98Sn98-2、Zn2-98Bi98-2、Zn5- 95Sb95-5、Zn2-98Pb98-2、Zn5-95Te95-5、Zn2-98Sn98-2Bi0-80、Zn2-98Sn98-2Sb0-90、Zn2-98Sn98-2Pb0-60、Zn2- 98Sn98-2Te0-60、Zn2-98Bi98-2Sb0-80、Zn2-98Bi98-2Pb0-50、Zn2-98Bi98-2Te0-60、Zn5-95Sb95-5Pb0-60、Zn5- 95Sb95-5Te0-70、Zn2-98Pb98-2Te0-60,其中,化学式中右下角标表示每种成分的摩尔百分比,且每种合金中各组分的摩尔百分比相加等于100%。Further, the molar percentages of the above-mentioned positive electrode materials are: Zn 2-98 Sn 98-2 , Zn 2-98 Bi 98-2 , Zn 5-95 Sb 95-5 , Zn 2-98 Pb 98-2 , Zn 5-95 Te 95-5 , Zn 2-98 Sn 98-2 Bi 0-80 , Zn 2-98 Sn 98-2 Sb 0-90 , Zn 2-98 Sn 98-2 Pb 0-60 , Zn 2- 98 Sn 98-2 Te 0-60 , Zn 2-98 Bi 98-2 Sb 0-80 , Zn 2-98 Bi 98-2 Pb 0-50 , Zn 2-98 Bi 98-2 Te 0-60 , Zn 5-95 Sb 95-5 Pb 0-60 , Zn 5- 95 Sb 95-5 Te 0-70 , Zn 2-98 Pb 98-2 Te 0-60 , where the lower right subscript in the chemical formula indicates the mole percentage, and the mole percentages of the components in each alloy add up to 100%.
进一步地,本发明的正极材料制备方法十分简单,在制备Zn合金时,按照所述摩尔百分比,称量金属Zn和其他所需的金属原料,简单混合后在惰性气氛保护或真空条件下加热到所述比例合金熔点以上50-100℃,并保温2-24h,使混合金属原料充分合金化,即可得到Zn合金正极材料。Furthermore, the preparation method of the cathode material of the present invention is very simple. When preparing the Zn alloy, weigh the metal Zn and other required metal raw materials according to the molar percentage, briefly mix and then heat to The melting point of the alloy in the above proportion is 50-100°C, and the temperature is maintained for 2-24 hours to fully alloy the mixed metal raw materials, and then the Zn alloy cathode material can be obtained.
本发明的另一方面提供了一种应用液态或半液态金属电池正极材料的储能电池,其组成包括壳体、负极集流体、负极、熔盐电解质、正极、正极集流体和陶瓷密封器件,熔融的负极液态金属吸附在负极集流体中,其中所述正极采用如上所述的正极材料。Another aspect of the present invention provides an energy storage battery using liquid or semi-liquid metal battery cathode materials, which consists of a casing, a negative electrode current collector, a negative electrode, a molten salt electrolyte, a positive electrode, a positive electrode current collector and a ceramic sealing device, The molten negative electrode liquid metal is adsorbed in the negative electrode current collector, wherein the positive electrode adopts the positive electrode material as described above.
进一步地,所述负极集流体为多孔泡沫材料。Further, the negative electrode current collector is a porous foam material.
进一步地,所述正极集流体为石墨、W、Mo材料中的一种。Further, the positive electrode current collector is one of graphite, W, and Mo materials.
进一步地,上述的储能电池,在工作温度下负极材料处于液态,正极和电解质材料处于液态或半液态。Furthermore, in the above-mentioned energy storage battery, the negative electrode material is in a liquid state at the operating temperature, and the positive electrode and electrolyte materials are in a liquid or semi-liquid state.
具体地,本发明提供的液态或半液态金属电池的装配方法十分简单,在氩气气氛保护下,在工作温度下,壳体内自下而上依序放置正极集流体、正极、熔盐电解质、负极组装电池,并通过陶瓷密封器件实现负极与壳体的绝缘。电池装配完成后,升温至工作温度进行电池性能测试。Specifically, the assembly method of the liquid or semi-liquid metal battery provided by the present invention is very simple. Under the protection of argon atmosphere and at working temperature, the positive current collector, positive electrode, molten salt electrolyte, and The negative electrode assembles the battery, and the negative electrode is insulated from the case through a ceramic sealing device. After the battery assembly is completed, the temperature is raised to the operating temperature for battery performance testing.
本发明的技术关键点在于:The technical key points of the present invention are:
1、Zn自身具有较低的熔点,与Sn、Bi、Sb、Pb、Te中的一种或多种单质合金化后也可以降低正极材料的熔点;将锌合金用作液态或半液态金属电池正极材料时,可以有效降低电池的工作温度。1. Zn itself has a low melting point. After alloying with one or more of Sn, Bi, Sb, Pb, and Te, it can also reduce the melting point of the cathode material; zinc alloys can be used as liquid or semi-liquid metal batteries. The positive electrode material can effectively reduce the operating temperature of the battery.
2、采用Zn,或者Zn与Sn、Bi、Sb、Pb、Te替代现有技术当中在Bi、Sb、Te等高性能正极材料中加入添加的Sn、Pb、Ga等第二组元,在电池放电初期,锌可以参与电极反应,生成LiZnX(X为Bi、Sb、Te中的一种)金属间化合物,具有较高的放电电压;随着放电的进行,LiZnX逐渐转化成Li-X固态金属间化合物,在此过程中重新生成的Zn弥散在金属间化合物层,可以作为锂快速扩散通道,加快锂与下层正极的反应,进一步提高了电极反应动力学。应用于储能电池后,解决了现有液态或半液态金属电池工作电压低、能量密度低、原料成本高等问题。2. Use Zn, or Zn and Sn, Bi, Sb, Pb, Te to replace the existing technology. Add the added second components such as Sn, Pb, Ga, etc. to the high-performance cathode materials such as Bi, Sb, Te, etc. in the battery. In the early stage of discharge, zinc can participate in the electrode reaction to generate LiZnX (X is one of Bi, Sb, and Te) intermetallic compounds, which have a high discharge voltage; as the discharge proceeds, LiZnX gradually transforms into Li-X solid metal During this process, the regenerated Zn is dispersed in the intermetallic compound layer, which can serve as a rapid diffusion channel for lithium, speeding up the reaction between lithium and the lower cathode, and further improving the electrode reaction kinetics. After being applied to energy storage batteries, it solves the problems of existing liquid or semi-liquid metal batteries such as low operating voltage, low energy density, and high raw material costs.
3、利用Zn具有较好的储锂能力的特点,在降低体系温度的同时,可以有效提高正极活性物质的利用率,提高电池的容量及能量密度。3. Utilizing Zn's good lithium storage capacity, it can effectively improve the utilization rate of the positive active material and increase the capacity and energy density of the battery while reducing the system temperature.
4、采用Zn,或者Zn与Sn、Bi、Sb、Pb、Te形成的合金,与采用LiF、LiCl及LiBr等原料制备的熔盐电解质及泡沫镍为负极集流体相匹配,制备得到的液态或半液态金属电池性能颇佳,其中以锌锑合金为正极材料制备得到的液态或半液态金属电池性能为最佳。4. Use Zn, or an alloy formed by Zn and Sn, Bi, Sb, Pb, Te, to match the molten salt electrolyte and nickel foam prepared from raw materials such as LiF, LiCl and LiBr as the negative electrode current collector. The prepared liquid or The performance of semi-liquid metal batteries is quite good, among which the liquid or semi-liquid metal batteries prepared with zinc-antimony alloy as the cathode material have the best performance.
基于本发明制备的电池测试结果表明,与现有技术相比,本发明的技术方案具有如下有益效果或技术优势:The battery test results prepared based on the present invention show that compared with the existing technology, the technical solution of the present invention has the following beneficial effects or technical advantages:
Zn自身具有较低的熔点,与Sn、Bi、Sb、Pb、Te中的一种或多种单质合金化后也可以降低正极材料的熔点;将锌合金用作液态或半液态金属电池正极材料时,可以有效降低电池的工作温度。Zn itself has a low melting point, and after alloying with one or more of Sn, Bi, Sb, Pb, and Te, it can also reduce the melting point of the cathode material; zinc alloys are used as cathode materials for liquid or semi-liquid metal batteries When, it can effectively reduce the operating temperature of the battery.
Zn具有较好的储锂能力,在降低体系温度的同时,可以保证正极活性物质的利用率,提高电池的容量及能量密度。Zn has good lithium storage capacity. While reducing the system temperature, it can ensure the utilization of the positive active material and increase the capacity and energy density of the battery.
本发明中金属Zn具有较低的电阻率(5.9×10-4Ωcm),将Zn或者Zn合金用作液态或半液态金属电池正极材料时,可以提高正极材料的导电性,改善电池的倍率性能,有效减小电池充放电过程中的极化,提高电池的放电电压。The metal Zn in the present invention has a low resistivity (5.9×10 -4 Ωcm). When Zn or Zn alloy is used as a positive electrode material of a liquid or semi-liquid metal battery, the conductivity of the positive electrode material can be improved and the rate performance of the battery can be improved. , effectively reducing the polarization during battery charging and discharging and increasing the battery's discharge voltage.
金属Zn和Zn合金成本低廉,制备工艺简单,无需特殊设备,将其用作液态或半液态金属电池正极材料时,可以减小电池原料和装配成本。Metal Zn and Zn alloys are low-cost, simple in preparation process, and do not require special equipment. When used as cathode materials for liquid or semi-liquid metal batteries, battery raw materials and assembly costs can be reduced.
附图说明Description of the drawings
图1是采用本发明正极材料的液态或半液态金属电池的结构示意图;Figure 1 is a schematic structural diagram of a liquid or semi-liquid metal battery using the cathode material of the present invention;
图2是采用本发明实施例1的液态金属储能电池充放电性能曲线;Figure 2 is a charging and discharging performance curve of a liquid metal energy storage battery using Embodiment 1 of the present invention;
图3是采用本发明实施例2的液态金属储能电池充放电性能曲线;Figure 3 is a charging and discharging performance curve of a liquid metal energy storage battery using Embodiment 2 of the present invention;
图4是采用本发明实施例3的液态金属储能电池充放电性能曲线;Figure 4 is a charging and discharging performance curve of a liquid metal energy storage battery using Embodiment 3 of the present invention;
图5是采用本发明实施例3的液态金属储能电池循环特性曲线。Figure 5 is a cycle characteristic curve of a liquid metal energy storage battery using Embodiment 3 of the present invention.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚明白,下面将结合附图和实施例对本发明实施方式进行进一步地详细描述。应当理解,此处所描述的具体实施例仅仅用于解释本发明,并不用于限制本发明。此外,以下描述的本发明的各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以互相组合。In order to make the purpose, technical solutions and advantages of the present invention more clear, the embodiments of the present invention will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described here are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
本发明针对现有液态或半液态金属电池工作电压低、能量密度低、原料成本和装配成本高等问题,提供了一种用于液态或半液态金属电池的正极材料,该正极材料为金属Zn,或者Zn与Sn、Bi、Sb、Pb、Te中的一种或多种单质形成的Zn合金,所述Zn合金的化学式为:Aiming at the problems of low operating voltage, low energy density, high raw material cost and high assembly cost of existing liquid or semi-liquid metal batteries, the present invention provides a cathode material for liquid or semi-liquid metal batteries. The cathode material is metal Zn. Or a Zn alloy formed by Zn and one or more of Sn, Bi, Sb, Pb, and Te. The chemical formula of the Zn alloy is:
Zn2-98Sn98-2、Zn2-98Bi98-2、Zn5-95Sb95-5、Zn2-98Pb98-2、Zn5-95Te95-5、Zn2-98Sn98-2Bi0-80、Zn2-98Sn98-2Sb0-90、Zn2-98Sn98-2Pb0-60、Zn2-98Sn98-2Te0-60、Zn2-98Bi98-2Sb0-80、Zn2-98Bi98-2Pb0-50、Zn2-98Bi98-2Te0-60、Zn5-95Sb95-5Pb0-60、Zn5-95Sb95-5Te0-70、Zn2-98Pb98-2Te0-60,其中,化学式中右下角标表示每种成分的摩尔百分比,且每种合金中各组分的摩尔百分比相加等于100%。Zn 2-98 Sn 98-2 , Zn 2-98 Bi 98-2 , Zn 5-95 Sb 95-5 , Zn 2-98 Pb 98-2 , Zn 5-95 Te 95-5 , Zn 2-98 Sn 98-2 Bi 0-80 , Zn 2-98 Sn 98-2 Sb 0-90 , Zn 2-98 Sn 98-2 Pb 0-60 , Zn 2-98 Sn 98-2 Te 0-60 , Zn 2- 98 Bi 98-2 Sb 0-80 , Zn 2-98 Bi 98-2 Pb 0-50 , Zn 2-98 Bi 98-2 Te 0-60 , Zn 5-95 Sb 95-5 Pb 0-60 , Zn 5-95 Sb 95-5 Te 0-70 , Zn 2-98 Pb 98-2 Te 0-60 , where the lower right subscript in the chemical formula indicates the mole percentage of each component, and the mole of each component in each alloy The percentages add up to 100%.
制备Zn合金时,按照所述摩尔百分比,称量金属Zn和其他所需的金属原料,放入石墨坩埚、陶瓷坩埚或者金属坩埚中简单混合均匀,再将盛有混合金属原料的坩埚放入管式炉或其他加热炉中,在惰性气氛保护或真空条件下,加热到所述比例合金熔点以上50-100℃,并保温2-24h,使混合金属原料充分合金化,即可得到正极合金材料。该正极材料的制备方法十分简单,无需特殊的设备,产量高,能够降低电极材料的制备成本。When preparing Zn alloy, weigh the metal Zn and other required metal raw materials according to the molar percentage, put them into a graphite crucible, ceramic crucible or metal crucible and simply mix them evenly, and then put the crucible containing the mixed metal raw materials into the tube. In a furnace or other heating furnace, under inert atmosphere protection or vacuum conditions, heat to 50-100°C above the melting point of the proportional alloy, and keep it for 2-24 hours to fully alloy the mixed metal raw materials, and then the cathode alloy material can be obtained . The preparation method of the positive electrode material is very simple, does not require special equipment, has high yield, and can reduce the preparation cost of the electrode material.
按照本发明的另一个方面,本发明还提供了一种应用该正极材料的液态或半液态金属储能电池,其结构示意图如图1所示,包括壳体1、正极集流体2、正极3、熔盐电解质4、负极5和陶瓷密封器件6,所述壳体1采用金属材料制成,为底端密封的金属筒,其内部自下而上依序放置正极集流体2、正极3、熔盐电解质4、负极5,负极5由吸附熔融液态负极金属的泡沫集流体构成,并通过陶瓷密封器件6与壳体1进行绝缘。其中所述正极采用如上所述的正极材料。According to another aspect of the invention, the invention also provides a liquid or semi-liquid metal energy storage battery using the cathode material. The schematic structural diagram is shown in Figure 1, including a casing 1, a cathode current collector 2, and a cathode 3. , molten salt electrolyte 4, negative electrode 5 and ceramic sealing device 6. The housing 1 is made of metal material and is a metal cylinder with a sealed bottom end. The positive electrode current collector 2, positive electrode 3, Molten salt electrolyte 4, negative electrode 5, the negative electrode 5 is composed of a foam current collector that absorbs molten liquid negative electrode metal, and is insulated from the case 1 by a ceramic sealing device 6. The positive electrode adopts the positive electrode material as mentioned above.
本发明提供的应用该正极材料的液态或半液态金属电池储能电池,熔融的负极液态金属吸附在负极集流体中,壳体内自下而上依序放置正极集流体、正极、熔盐电解质、负极组装电池,并通过陶瓷密封器件实现负极与壳体的绝缘。所述负极集流体为多孔泡沫材料,所述正极集流体为石墨、W、Mo材料中的一种。In the liquid or semi-liquid metal battery energy storage battery using the positive electrode material provided by the invention, the molten negative electrode liquid metal is adsorbed in the negative electrode current collector, and the positive electrode current collector, positive electrode, molten salt electrolyte, and The negative electrode assembles the battery, and the negative electrode is insulated from the case through a ceramic sealing device. The negative electrode current collector is a porous foam material, and the positive electrode current collector is one of graphite, W, and Mo materials.
本发明提供的应用该正极材料的液态或半液态金属电池储能电池,其装配过程如下:首先,将负极泡沫金属集流体放置于熔融的负极金属中,根据所需比例,使负极集流体吸附一定质量的负极金属,完成负极的制备;然后,将正极集流体放置入电池壳体中,电池壳体置于加热炉中,并加热到工作温度;随后依次放入正极、熔盐电解质并保温0.5-2h,待正极与熔盐电解质完全熔化后,将制备的负极浸入电解质中,调整负极与正极的间距为10-20mm,最后,将电池冷却至室温,完成电池密封,电池装配过程完成。整个电池装配过程在充满氩气气氛的手套箱内完成。The assembly process of the liquid or semi-liquid metal battery energy storage battery using the positive electrode material provided by the present invention is as follows: first, place the negative electrode foam metal current collector in the molten negative electrode metal, and make the negative electrode current collector adsorb according to the required ratio. A certain quality of negative electrode metal is used to complete the preparation of the negative electrode; then, the positive electrode current collector is placed into the battery case, and the battery case is placed in the heating furnace and heated to the operating temperature; then the positive electrode, molten salt electrolyte is placed in sequence and kept warm 0.5-2h, after the positive electrode and molten salt electrolyte are completely melted, immerse the prepared negative electrode in the electrolyte, adjust the distance between the negative electrode and the positive electrode to 10-20mm, and finally, cool the battery to room temperature, complete the battery sealing, and the battery assembly process is completed. The entire battery assembly process is completed in a glove box filled with argon atmosphere.
进一步地,本发明给出了一系列实施例,并结合附图对本发明进行进一步描述。采用各实施例的液态或半液态金属储能电池的结构及装配过程均相同,只不过每个实施例中正、负极材料和熔盐电解质的组成及制备过程有所不同。Further, the present invention provides a series of embodiments and further describes the present invention with reference to the accompanying drawings. The structures and assembly processes of the liquid or semi-liquid metal energy storage batteries used in each embodiment are the same, except that the compositions and preparation processes of the positive and negative electrode materials and molten salt electrolytes are different in each embodiment.
实施例1Example 1
本实施例以纯锌为正极材料,金属锂为负极材料,且正极材料与负极材料的摩尔比为1:1.05,电解质采用LiF、LiCl及LiBr组成的低熔点熔盐,其中LiF、LiCl及LiBr的摩尔百分比为22:31:47。金属锌具有低廉的原料成本(0.15$mol-1),远低于其他正极材料,因而本实施例的原料成本将大幅度降低。In this embodiment, pure zinc is used as the positive electrode material, and metallic lithium is used as the negative electrode material. The molar ratio of the positive electrode material to the negative electrode material is 1:1.05. The electrolyte uses a low melting point molten salt composed of LiF, LiCl and LiBr, where LiF, LiCl and LiBr are The molar percentage is 22:31:47. Metal zinc has a low raw material cost (0.15$mol -1 ), which is much lower than other cathode materials. Therefore, the raw material cost of this embodiment will be greatly reduced.
本实施例选用泡沫镍为负极集流体,将所需质量的熔融的金属锂吸附在泡沫镍中完成负极制备。正极集流体为石墨坩埚。在装配过程中,调整负极与正极的间距为16mm。In this embodiment, nickel foam is used as the negative electrode current collector, and the required mass of molten metal lithium is adsorbed in the nickel foam to complete the preparation of the negative electrode. The positive current collector is a graphite crucible. During the assembly process, adjust the distance between the negative electrode and the positive electrode to 16mm.
本实施例的电池工作温度为550℃,测试的电化学窗口为0.3-1.5V。图2为采用本发明实施例1的储能电池的充放电性能曲线。该电池具有良好的电化学性能,在200mA cm-2电流密度下,其放电中值电压高达0.54V,库仑效率为90.3%,能量效率为70%。同时,由于金属锌具有较低的相对原子质量,将其用作正极材料,可大幅度提高电池的能量密度,本实施例电池能量密度高达193Wh kg-1(基于正负极材料计算)。The operating temperature of the battery in this embodiment is 550°C, and the electrochemical window of the test is 0.3-1.5V. Figure 2 is a charge and discharge performance curve of the energy storage battery using Embodiment 1 of the present invention. The battery has good electrochemical properties, with a median discharge voltage as high as 0.54V, a Coulombic efficiency of 90.3%, and an energy efficiency of 70% at a current density of 200mA cm -2 . At the same time, because metallic zinc has a low relative atomic mass, using it as a positive electrode material can greatly increase the energy density of the battery. The energy density of the battery in this embodiment is as high as 193Wh kg -1 (calculated based on the positive and negative electrode materials).
实施例2Example 2
本实施例以锌锑合金为正极材料,金属锌、锑的摩尔百分比为70:30。金属锂为负极材料,且nLi=3*nSb+0.6*nZn。电解质采用LiF、LiCl及LiBr组成的低熔点熔盐,其中LiF、LiCl及LiBr的摩尔百分比为22:31:47。In this embodiment, a zinc-antimony alloy is used as the cathode material, and the molar percentage of metal zinc and antimony is 70:30. Metal lithium is the negative electrode material, and n Li =3*n Sb +0.6*n Zn . The electrolyte uses a low-melting point molten salt composed of LiF, LiCl and LiBr, where the molar percentage of LiF, LiCl and LiBr is 22:31:47.
本实施例的锌锑合金制备过程为:按照所述摩尔百分比称量金属Zn和Sb,放入石墨坩埚中简单混合均匀,再将盛有混合金属原料的坩埚放入管式炉中,在惰性气氛保护下,加热到600℃,并保温5h,即可得到所需锌锑合金。The preparation process of the zinc-antimony alloy in this embodiment is as follows: weigh the metal Zn and Sb according to the molar percentages, put them into a graphite crucible and mix them briefly, then put the crucible containing the mixed metal raw materials into a tube furnace, and inert Under atmosphere protection, heat to 600°C and keep warm for 5 hours to obtain the required zinc-antimony alloy.
本实施例选用泡沫镍为负极集流体,将所需质量的熔融的金属锂吸附在泡沫镍中完成负极制备。正极集流体为石墨坩埚。在装配过程中,调整负极与正极的间距为12mm。In this embodiment, nickel foam is used as the negative electrode current collector, and the required mass of molten metal lithium is adsorbed in the nickel foam to complete the preparation of the negative electrode. The positive current collector is a graphite crucible. During the assembly process, adjust the distance between the negative electrode and the positive electrode to 12mm.
本实施例的电池工作温度为550℃,测试的电化学窗口为0.3-1.5V。图3是采用本发明实施例2的电池的充放电性能曲线。从图3中可以看出,在100mA cm-2电流密度下,该电池在放电初期1V的高电压下具有一个的短暂平台。在整个放电过程中,电池的放电中值电压高达0.76V,能量密度高达293Wh kg-1(基于正负极材料计算)。此外,在此电流密度下,电池的库仑效率为82.3%,能量效率为75%,具有较为优异的电化学性能。The operating temperature of the battery in this embodiment is 550°C, and the electrochemical window of the test is 0.3-1.5V. Figure 3 is a charge and discharge performance curve of the battery using Embodiment 2 of the present invention. As can be seen from Figure 3, at a current density of 100mA cm -2 , the battery has a short-term plateau at a high voltage of 1V in the early stage of discharge. During the entire discharge process, the battery's median discharge voltage is as high as 0.76V, and its energy density is as high as 293Wh kg -1 (calculated based on positive and negative electrode materials). In addition, at this current density, the Coulombic efficiency of the battery is 82.3%, the energy efficiency is 75%, and it has excellent electrochemical performance.
实施例3Example 3
本实施例以锌铋合金为正极材料,金属锌、铋的摩尔百分比为30:70。金属锂为负极材料,且nLi=3*nBi+0.6*nZn。电解质采用LiF、LiCl及LiBr组成的低熔点熔盐,其中LiF、LiCl及LiBr的摩尔百分比为22:31:47。In this embodiment, a zinc-bismuth alloy is used as the cathode material, and the molar percentage of metal zinc and bismuth is 30:70. Metal lithium is the negative electrode material, and n Li =3*n Bi +0.6*n Zn . The electrolyte uses a low-melting point molten salt composed of LiF, LiCl and LiBr, where the molar percentage of LiF, LiCl and LiBr is 22:31:47.
本实施例的锌铋合金制备过程为:按照所述摩尔百分比称量金属Zn和Bi,放入石墨坩埚中简单混合均匀,再将盛有混合金属原料的坩埚放入管式炉中,在惰性气氛保护下,加热到550℃,并保温3h,即可得到所需锌铋合金。The preparation process of the zinc-bismuth alloy in this embodiment is as follows: weigh the metal Zn and Bi according to the molar percentages, put them into a graphite crucible and mix them briefly, then put the crucible containing the mixed metal raw materials into a tube furnace, and place them in an inert furnace. Under atmosphere protection, heat to 550°C and keep warm for 3 hours to obtain the required zinc-bismuth alloy.
本实施例选用泡沫镍铁为负极集流体,将所需质量的熔融的金属锂吸附在泡沫镍中完成负极制备。正极集流体为石墨坩埚。在装配过程中,调整负极与正极的间距为15mm。In this embodiment, foamed nickel iron is used as the negative electrode current collector, and the required mass of molten metal lithium is adsorbed in the nickel foam to complete the preparation of the negative electrode. The positive current collector is a graphite crucible. During the assembly process, adjust the distance between the negative electrode and the positive electrode to 15mm.
本实施例的电池工作温度为500℃,测试的电化学窗口为0.3-1.5V。图4是采用本发明实施例3的电池充放电性能曲线。本实施例3的电池具有较为优异的电化学性能,在200mA cm-2电流密度下,放电电压高达0.73V,库仑效率为91.3%,能量效率为78%。图5是采用本发明实施例3的电池循环性能曲线,在800mAcm-2电流密度下充放电循环50圈,库仑效率一直保持在98%以上,容量衰减率仅为每圈0.12%。The operating temperature of the battery in this embodiment is 500°C, and the electrochemical window of the test is 0.3-1.5V. Figure 4 is a battery charge and discharge performance curve using Embodiment 3 of the present invention. The battery of Example 3 has relatively excellent electrochemical properties. At a current density of 200 mA cm -2 , the discharge voltage is as high as 0.73V, the Coulombic efficiency is 91.3%, and the energy efficiency is 78%. Figure 5 is a battery cycle performance curve using Embodiment 3 of the present invention. After 50 charge and discharge cycles at a current density of 800 mAcm -2 , the Coulomb efficiency has remained above 98%, and the capacity attenuation rate is only 0.12% per cycle.
以上测试结果表明:本发明的正极材料应用于液态或半液态金属电池中,提高了液态或半液态金属电池的工作电压,得到了较高的库仑效率和能量密度,电池循环性能良好;同时,低成本的Zn在液态或半液态金属电池中的成功应用,降低了电池的储能成本。The above test results show that the cathode material of the present invention is used in liquid or semi-liquid metal batteries, improves the operating voltage of liquid or semi-liquid metal batteries, obtains higher Coulombic efficiency and energy density, and has good battery cycle performance; at the same time, The successful application of low-cost Zn in liquid or semi-liquid metal batteries has reduced the energy storage cost of batteries.
以上所述是本发明的优选实施方式,不用于限制本发明。应当指出,本发明对于本技术领域的技术人员来说容易理解,因此在本发明所述原理基础上做出若干替换、改进和润饰也应视为本发明的保护范围。The above descriptions are preferred embodiments of the present invention and are not intended to limit the present invention. It should be noted that the present invention is easy to understand for those skilled in the art, and therefore several substitutions, improvements and modifications made on the basis of the principles described in the present invention should also be regarded as the protection scope of the present invention.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103259004A (en) * | 2013-04-16 | 2013-08-21 | 华中科技大学 | Anode material for liquid-state and semi-liquid-state metal energy-storing batteries |
CN104124459A (en) * | 2014-07-22 | 2014-10-29 | 西安交通大学 | Square liquid metal battery device and assembling method thereof |
CN110729470A (en) * | 2019-10-22 | 2020-01-24 | 北京科技大学 | Positive electrode material of liquid or semi-liquid metal battery, preparation method and application |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103259004A (en) * | 2013-04-16 | 2013-08-21 | 华中科技大学 | Anode material for liquid-state and semi-liquid-state metal energy-storing batteries |
CN104124459A (en) * | 2014-07-22 | 2014-10-29 | 西安交通大学 | Square liquid metal battery device and assembling method thereof |
CN110729470A (en) * | 2019-10-22 | 2020-01-24 | 北京科技大学 | Positive electrode material of liquid or semi-liquid metal battery, preparation method and application |
Non-Patent Citations (5)
Title |
---|
Aqueous Zinc–Tellurium Batteries with Ultraflat Discharge Plateau and High Volumetric Capacity;Ze Chen等;《advanced materials》;第1-9页 * |
Low-temperature and high-voltage Zn-based liquid metal batteries based on multiple redox mechanism;Wang Zhao 等;《Journal of Power Sources》;20200428;第1-10页 * |
Low-temperature and high-voltage Zn-based liquid metal batteries based on multiple redox mechanism;Wang Zhao 等;《Journal of PowerSources》;第228-233页 * |
The effects of mechanical alloying on the self-discharge and corrosion behavior in Zn-air batteries;Yong Nam Jo 等;《Journal of Industrial and Engineering Chemistry》;第247-252页 * |
新型液态金属电池正极材料的探索研究;徐丽 等;《材料科学与工艺》;20210430;第29卷(第2期);第20-26页 * |
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