WO2014153957A1 - Water-based alkali metal ion energy storage device - Google Patents

Water-based alkali metal ion energy storage device Download PDF

Info

Publication number
WO2014153957A1
WO2014153957A1 PCT/CN2013/086064 CN2013086064W WO2014153957A1 WO 2014153957 A1 WO2014153957 A1 WO 2014153957A1 CN 2013086064 W CN2013086064 W CN 2013086064W WO 2014153957 A1 WO2014153957 A1 WO 2014153957A1
Authority
WO
WIPO (PCT)
Prior art keywords
energy storage
sodium
alkali metal
storage device
potassium
Prior art date
Application number
PCT/CN2013/086064
Other languages
French (fr)
Chinese (zh)
Inventor
方淳
袁超群
戴翔
Original Assignee
恩力能源科技（南通）有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 恩力能源科技（南通）有限公司 filed Critical 恩力能源科技（南通）有限公司
Publication of WO2014153957A1 publication Critical patent/WO2014153957A1/en

Links

Classifications

    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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

Definitions

  • the present invention relates to an aqueous alkali metal ion electrochemical energy storage device. Background technique
  • electrochemical energy storage can adapt to different grid function needs, and it has advantages in integrated grid connection of wind power and photovoltaic.
  • the way for energy storage in large-scale power grids is based on traditional lead-acid batteries.
  • Lead-acid batteries have low cost, but short life, and major materials such as lead and concentrated sulfuric acid cause serious pollution to the environment and require recycling. Therefore, there is an urgent need to find a new technology that can replace lead-acid batteries.
  • the positive electrode material of the hybrid water-based lithium ion battery is LiMn 2 0 4 , LiCo0 2 , LiCo 1/3 M 1/3 Mn 1/3 0 2 , LiMgo.2Mm.8O4 can reversibly intercalate lithium ion-extracting materials, and the negative electrode uses activated carbon, mesoporous carbon or carbon nanotubes having a specific surface area of 1000 m 2 /g or more.
  • CN102027625A discloses an aqueous phase electrolyte electrochemical secondary energy storage device mainly composed of sodium ions, which comprises an anode electrode, a cathode electrode capable of reversibly deintercalating sodium cations, a separator and a sodium cation.
  • An aqueous electrolyte wherein the initial active cathode electrode material comprises an alkali metal-containing active cathode electrode material that deintercalates alkali metal ions during initial charging of the device.
  • the active cathode electrode material may be aluminum-doped ⁇ - ⁇ 0 2 , NaMn0 2 (sodium manganite structure), Na 2 Mn 3 0 7 NaFeP0 4 F Na 0 . 44 MnO 2 .
  • the anode electrode comprises porous activated carbon and the electrolyte comprises sodium sulfate.
  • Chinese Patent Publication No. CN1723578A discloses a sodium ion battery comprising a positive electrode, a negative electrode and an electrolyte.
  • the positive electrode includes an electrochemically active material capable of reversibly circulating sodium ions
  • the negative electrode includes a carbon capable of intercalating sodium ions.
  • the active material includes a sodium transition metal phosphate.
  • the transition metal includes a transition metal selected from the group consisting of vanadium (v), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), nickel (M), and titanium (Ti), and mixtures thereof.
  • CN101241802A discloses an asymmetric water-based sodium/potassium battery capacitor composed of a positive electrode, a negative electrode, a separator and an electrolyte.
  • the active materials of the positive electrode are NaMn0 2 , NaCo0 2 , NaV 3 0 8 , NaVP0 4 F, and Na 2 VOP0 4 .
  • the positive electrode active material is uniformly mixed with carbon black and a binder, coated on a nickel mesh current collector, dried and pressed into an electrode.
  • the activated carbon is mixed with a conductive agent and a binder, uniformly coated on a nickel mesh current collector, dried and pressed into an electrode.
  • a non-woven fabric was used as a separator, and sodium chloride or sodium sulfate was used as an electrolyte to assemble a battery.
  • the above-mentioned phosphate positive electrode material having a spinel structure and a menorite structure or a core-shell structure although having a theoretical specific capacity of more than 100 mAh/g, is contained in sodium/potassium ions.
  • the effective recyclable specific capacity in the aqueous solution is below 100 mAh/g, resulting in low energy density of the device, which becomes a bottleneck for the promotion of sodium/potassium ion storage technology. It is urgent to develop a new positive electrode material with high capacity, thereby improving Energy density of sodium/potassium energy storage devices.
  • the present invention provides an aqueous alkali metal ion electrochemical energy storage device comprising a positive electrode, a negative electrode, a separator, and an alkali metal ion-containing water.
  • the active material of the positive electrode is an alkali metal-containing multicomponent transition metal oxide having the general formula A 1+a (X m Y n M ni _ m _ n ) 0 2+b , wherein A is selected From one or more of Li, Na and K; X, Y is selected from one of M, Co, Al, Cr, V, Ti and Fe; 0 ⁇ m+n ⁇ l; 0 ⁇ a, b ⁇ 1, in the aqueous phase electrolyte containing sodium or potassium salt, the crystal structure of the multi-element transition metal oxide of the active material of the positive electrode contains a layered structure, and the positive electrode has an effective specific capacity of more than 100 mAh/g.
  • the active material of the negative electrode may be selected from one or more of activated carbon, graphene, carbon nanotubes, carbon fibers, and mesoporous carbon, and these materials are all large.
  • the surface area is subjected to an illegally drawn electric double layer electron adsorption process, and the positive electrode is composed of a hybrid capacitor battery.
  • It may also be selected from materials capable of performing a reversible redox reaction containing a Faraday electron transfer process in an aqueous phase electrolyte.
  • Such materials include oxides, phosphate materials that are capable of reversible intercalation and deintercalation of alkali metal ions.
  • the crystal structure of the alkali metal multi-element transition metal oxide of the positive electrode material contains a layered structure.
  • the alkali metal-containing multicomponent transition metal oxide is selected from the group consisting of LiNio.33Coo.33Mno.33O2, LiNio.4Coo.2Mno.4O2, LiNio.5Coo.2Mno.3O2, LiNio.5Mno.5O2, NaNio.33Coo.33Mno.33O2, NaNio .4Coo.2Mno.4O2, NaNio.5Coo.2Mno.3O2, NaNio.5Mno.5O2, KNio.33Coo.33Mno.33O2 KNio.5Coo.2Mno.3O2 KNio.4Coo.2Mno.4O2 KNio.5Mno.5O2 a mixture of one or more of them, or a metal or non-metal element doped material of the above transition metal oxide.
  • the doping metal contains one or more of Li, Mg, Al, Cu, Cr, Mg, Zr, Fe, and Mo.
  • Doped non-metallic package Contain? One or more of Si, B, and B.
  • the aqueous phase electrolyte solution includes, but is not limited to, sodium sulfate, sodium nitrate, sodium halide, sodium carbonate, sodium phosphate, sodium acetate, sodium hydroxide, sodium perchlorate. And a mixture of one or more of potassium sulfate, potassium nitrate, potassium halide, potassium carbonate, potassium phosphate, potassium acetate, potassium hydroxide, potassium perchlorate.
  • the electrolyte concentration is 0.5 - 10 mol and the pH is between 3 and 12.
  • the present invention provides an alkali metal-containing multi-element transition metal oxide cathode material.
  • the alkali metal-containing multicomponent transition metal oxide of the present invention has a general formula Wherein A is selected from one or more of Li, Na and K; X and ⁇ are selected from ⁇ , 0, 1, 0 ⁇ ⁇ , 1 and ? One of 6; 0 ⁇ m+n ⁇ l; 0 ⁇ a, b ⁇ l.
  • the alkali metal-containing multicomponent transition metal oxide is selected from the group consisting of LiM 33 Co 33 MnQ. 33 0 2 , LiNio. 4 Coo. 2 Mno. 4 O 2 , Li Nio. 5 Coo. 2 Mno. 3 O 2 , Li Nio. 5 Mno. 5 O 2 , NaNio.
  • the positive electrode material also needs to add 1% - 10% of conductive agent (graphite, carbon black, acetylene black, etc.) to improve the conductivity of the material, and also needs to add 1% - 10% of the binder (polytetrafluoroethylene, Polyvinylidene fluoride or the like is used to form a uniform, viscous mixed material, and the mixed material is fixed to the collector by pressure or conductive paste.
  • the collector includes stainless steel, nickel, titanium, graphite fiber cloth, and the like.
  • the alkali metal-containing multi-element transition metal oxide positive electrode material has a spheroidal shape, and is characterized in that the spheroidal particles are secondary particles formed by agglomeration of primary particles of nanostructures.
  • the nano-sized primary particles have an average particle diameter of less than 500 nm
  • the spheroidal secondary particles have an average particle diameter in the range of 1 micrometer to 20 micrometers.
  • the precursor of the alkali metal-containing multicomponent transition metal oxide positive electrode material is prepared by a synthetic method of coprecipitation. The biggest feature of this synthesis method is that it is easy to industrialize. Compared with sol-gel method, hydrothermal method and microwave method, although it has been widely used in the synthesis of nano-materials in laboratory-scale synthesis in recent years, due to the high cost of raw materials, complicated process, harsh synthesis conditions, synthesis cycle Long issues are not suitable for large-scale industrialization.
  • the active material of the positive electrode is an alkali metal-containing multicomponent transition metal oxide having the general formula A 1+a (X m Y n M ni _ m _ n ) 0 2+b , wherein the alkali metal A contains lithium (Li And the active material containing the lithium positive electrode undergoes chemical or electrochemical alkali metal ion exchange treatment before or after assembly of the aqueous electrochemical energy storage device.
  • the active material containing the lithium positive electrode can be chemically treated before the device is assembled, and the active material is placed in a dilute acid solution. Immersion is performed to detach lithium ions.
  • the active material of the lithium-containing positive electrode is subjected to electrochemical alkali metal ion exchange treatment, and the active material is placed in an electrochemical cell containing a sodium or potassium salt solution, and a long-term charge and discharge cycle is performed in a certain voltage range to cause lithium ions to pass from
  • the structure of the positive electrode material is removed, and sodium or potassium ions are introduced into the structure of the positive electrode material, thereby achieving exchange between sodium or potassium ions and lithium ions.
  • the electrochemical alkali metal ion exchange treatment can be carried out before the device is assembled, or can be realized by performing charge and discharge activation after the device is assembled.
  • FIG. 1 is a structural view of a positive electrode active material in the first embodiment of the present invention, which is a LiNi 5 Co 2 Mn 3 0 2 -activated carbon energy storage device.
  • Fig. 2 is a graph showing charge and discharge curves of a LiNi 5 Co 2 Mn 3 0 2 -activated carbon energy storage device in an aqueous solution of sodium sulfate in Example 1 of the present invention.
  • Fig. 3 is a graph showing charge and discharge curves of a LiNi 5 Co 2 Mn 3 0 2 -activated carbon energy storage device in an aqueous solution of potassium sulfate in Example 1 of the present invention.
  • Fig. 4 is a graph showing charge and discharge curves of a LiNi 5 Co 2 Mn 3 0 2 -activated carbon energy storage device in an aqueous solution of sodium nitrate in Example 1 of the present invention.
  • Fig. 3 is a graph showing charge and discharge curves of a LiNi 5 Co 2 Mn 3 0 2 -activated carbon energy storage device in an aqueous solution of sodium nitrate in Example 1 of the present invention.
  • FIG. 5 is a graph showing the cycle performance of a LiNi 5 Co 2 Mn 3 0 2 -activated carbon energy storage device in an aqueous solution of sodium nitrate in Example 1 of the present invention.
  • the first to tenth cycles were charged and discharged at 0.1 C, and after the tenth cycle, charged and discharged at 1 C.
  • Figure 6 is an X-ray powder diffraction (XRD) pattern of LiM Q . 5 Co 2 Mn 3 0 2 in Example 1 of the present invention.
  • Fig. 7 is a view showing LiM in the first embodiment of the present invention. . 5 Co. 2 Scanning electron microscopy (SEM) image of Mn 3 0 2 .
  • SEM Scanning electron microscopy
  • Figure 8 is a graph showing the charge and discharge curves of a LiNi 33 Co 33 Mn 33 0 2 -activated carbon energy storage device in an aqueous solution of sodium sulfate in Example 2 of the present invention.
  • Figure 9 is a diagram showing the LiNi 4 Co 2 Mn 4 0 2 -activated carbon energy storage device in the potassium sulfate aqueous solution in Example 3 of the present invention; The charge and discharge curve.
  • BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail by way of examples, but the scope of the invention is not limited thereto.
  • Example 1 A positive electrode active material was commercialized LiM Q . 5 Co 2 Mn 3 0 2 .
  • the separator is a hydrophilically treated PP-based separator, and the electrolytes are respectively 1M Na 2 S0 4 , 0.5MK 2 SO 4 , 2M NaN0 3 aqueous solution.
  • the structure of the battery is shown in Figure 1.
  • the reversible cycle charge and discharge curves are shown in Figures 2, 3 and 4, respectively. In the voltage range of 0.2V-1.8V, the charge and discharge current is 0.1C, in Na 2 S0 4 , K 2 S0 4.
  • the specific capacity of reversible cyclic discharge in NaN0 3 solution is 120.5 mAh/g, 148.0 mAh/g, and 120.9 mAh/g, respectively.
  • the discharge cycle curve in a 2M NaN0 3 aqueous solution is shown in Fig. 5.
  • Figure 6 is an X-ray powder diffraction (XRD) pattern of LiM Q . 5 Co 2 Mn 3 0 2 in Example 1 of the present invention.
  • Figure 7 is a scanning electron microscope (SEM) image of LiM Q . 5 Co 2 M n 3 0 2 in Example 1 of the present invention.
  • Figure 7 shows that the alkali metal-containing multi-element transition metal oxide cathode material has a spheroidal shape, and the spherical particles are secondary particles formed by agglomeration of nanostructured primary particles, wherein the average particle of the nano-sized primary particles The diameter is less than 500 nm, and the average particle diameter of the spheroidal secondary particles is in the range of 1 micrometer to 20 micrometers.
  • Example 2 A positive electrode active material was used as a commercial LiM Q . 33 Co 33 Mn 33 0 2 .
  • the separator is a hydrophilically treated PP-based separator, and the electrolyte is a 1 M Na 2 S0 4 aqueous solution.
  • the charge and discharge curves are respectively shown in FIG. 8 .
  • the charge and discharge current is 0.1 C, and the specific capacity of the reversible cyclic discharge in the Na 2 SO 4 aqueous solution is 122.1 mAh/g.
  • Example 3 A positive electrode active material was commercialized LiM 4Co 2 Mn 4 0 2 .
  • the separator is made of a hydrophilically treated PP-based separator, and the electrolyte is 0.5MK 2 S0 4 aqueous solution.
  • the charge-discharge curve is shown in Fig. 9.
  • the reversible cyclic discharge specific capacity with a discharge current of 0.1C is 118.4 mAh/g.
  • Table 1 below shows the reversible cyclic discharge specific capacity of different alkali metal-containing transition metal oxides and mono-port transition metal oxides (LiMn 2 0 4 and Na Q .44Mn0 2 ) in an aqueous solution containing Na, K metal salts. Comparison.
  • the active material of the negative electrode material is activated carbon.
  • the charge and discharge current (magnification) is 0.1C, and the charge and discharge voltage range is 0.2-1.8 V.
  • Table 1 Reversible cyclic discharge specific capacity positive electrode material electrolyte
  • LiNio.33Coo.33Mno.3302 1 M Na 2 S0 4 122.1
  • LiNio.4Coo.2Mno.402 0.5 MK 2 S0 4 118.4

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to a water-based alkali metal ion energy storage device, comprising an anode, a cathode, a separator, and an aqueous electrolyte solution containing alkali metal ions, characterized in that the anode active material is a multi-element transition metal oxide containing alkali metal and having a general formula of A1+a (XmYnMn1-m-n) O2+b, wherein A is selected from one or more of Li, Na and K; X and Y are selected from one of Ni, Co, Al, Cr, V, Ti, and Fe, 0<m+n<1, 0≤a and b<1; the crystal structure of the multi-element transition metal oxide of the anode active material has a layered structure, and is reversibly recycled at a capacity greater than 100 mAh/g. The water-based alkali metal electrochemical energy storage device has high capacity and low cost, is safe and environmentally friendly, and can be used in energy storage devices of various sizes.

Description

一种水系碱金属离子储能器件 技术领域 本发明涉及一种水系碱金属离子电化学储能器件。 背景技术  TECHNICAL FIELD The present invention relates to an aqueous alkali metal ion electrochemical energy storage device. Background technique
随着科技、 经济和社会的发展， 能源和环境问题越来越受到关注， 能源方面需 求持续暴涨，化石能源的短缺和对环境造成的破坏使关注点转向了风能、太阳能这些 可再生资源， 然而这些可再生能源受天气及时间段的影响较大， 具有明显的不稳定、 不连续和不可控等特点， 需要开发和建设配套的电能储存 （储能） 装置来保证发电、 供电的连续性和稳定性。 因此， 大规模储能技术是大力发展太阳能、风能等可再生能 源利用和智能电网的关键。在所有的储能技术中， 电池可以实现化学能与电能之间的 高效转换， 是一种最佳的能量储存技术。二次可充电池是目前使用最广泛的一种储能 方式。 与其它储能方式相比， 电化学储能能够适应不同的电网功能需要， 在风电、 光 电等的集成并网方面尤其具有优势。对于可充电池储能技术的推广方面来说，存在这 两大挑战。 第一是开发具有高电压和高能量的电池系统， 第二是使用成本低、 稳定、 对环境完全友好、长寿命的电池体系， 以保证源源不断的电能从可再生清洁能源中整 合到电网中。 目前， 用于大型电网储能的方式， 在实际布建的案例中， 还是以传统的铅酸电 池为主。铅酸电池成本低、但是寿命短、铅和浓硫酸等主要材料对环境造成严重污染， 需要回收。 因此， 迫切需要找到一种可以替代铅酸电池的新技术。 近二十年来， 锂离子电池技术的发展日益成熟， 由于其能量密度大， 输出电压 高， 使得锂离子电池在不同领域的应用也得到了迅猛发展。但是由于锂离子电池使用 有机溶剂作为电解液， 由此造成了制造成本偏高以及在使用中有易燃易爆的安全隐 患。中国专利授权公告号 CN1328818C公开了一种混合型水系锂离子电池。其工作原 理是： 对装成的电池， 首先必须进行充电。 充电过程中， 锂离子从正极脱出， 通过电 解液， 锂离子吸附在活性碳等材料做成的负极。 放电过程中， 锂离子从负极上脱附， 通过电解液， 锂离子嵌入正极。 充放电过程仅涉及锂离子在两电极间的转移。 该混合 型水系锂离子电池的正极材料采用 LiMn204、 LiCo02、 LiCo1/3M1/3Mn1/302、 LiMgo.2Mm.8O4等能够可逆的嵌入脱出锂离子的材料， 负极则采用比表面积在 1000m2/g以上的活性炭、 介孔碳或碳纳米管等。 另外， 随着锂离子电池的大规模应用， 锂的需求量会越来越大， 由于地壳中有 限的储量， 导致锂材料的价格会越来越高。近年来人们开始关注用更为廉价的碱金属 如钠， 钾甚至是碱土金属镁来取代锂用于储能器件。钠在地壳中的储量非常丰富， 约 占 2.74 %， 为第六丰富元素， 分布广泛， 含钠的原料价格较低； 以及和锂相似的电化 学性质， 钠基的电池渐渐成为了锂离子电池的替代选择。 早期研究的基于钠金属的钠硫和 Na/ Cl2电池，虽然具有较为理想的能量密度， 但是要用到熔融态的钠作为负极， 运行温度在 300〜350°C之间， 因此需要配套使用 高额的热管理体系和特殊的陶瓷固体电解质。另外如果陶瓷固体电解质一旦破损形成 短路， 高温的液态钠和硫就会直接接触， 发生剧烈的放热反应， 产生 2000°C的高温， 有较大的安全隐患。 基于这些背景和原因， 室温钠离子电池又成为人们的研究热点。 中国专利公开号 CN102027625A公开了一种以钠离子为主的水相电解质电化学 二次能源储存装置， 其包括阳极电极、 能够使钠阳离子可逆性脱嵌的阴极电极、 隔板 和含有钠阳离子的水相电解质，其中初始活性阴极电极材料包含在该装置的初始充电 期间使碱金属离子脱嵌的含碱金属的活性阴极电极材料。该活性阴极电极材料可以是 掺铝的 λ-Μη02、 NaMn02(水钠锰矿结构）、 Na2Mn307 NaFeP04F Na0.44MnO2。 该 阳极电极包含多孔活性炭， 且电解质包含硫酸钠。 中国专利公开号 CN1723578A公开了一种钠离子电池， 包括正电极、 负电极和 电解质。正电极包括一种能够可逆性循环钠离子的电化学活性材料， 负电极包括一种 能够嵌入钠离子的碳。该活性材料包括钠过渡金属磷酸盐。过渡金属包括选自钒（v)、 锰 （Mn)、 铁 （Fe)、 钴 （Co)、 铜 （Cu)、 镍 （M)、 钛 （Ti) 中的一种过渡金属及其 混合物。 中国专利公开号 CN101241802A 公开了一种非对称型水系钠 /钾离子电池电容 器，由正极、负极、隔膜和电解质组成。正极的活性材料为 NaMn02、NaCo02、NaV308、 NaVP04F和 Na2VOP04。将正极活性材料与炭黑、粘结剂混合均匀， 涂布在镍网集流 体上，烘干后压成电极。将活性炭与导电剂和粘结剂混合，均匀涂布在镍网集流体上， 烘干后压成电极。采用无纺布作为隔膜，用氯化钠或硫酸钠作为电解液，组装成电池。 但是， 以上被研究的具有尖晶石结构和水钠锰矿结构锰酸盐或具有核壳结构的 磷酸盐正极材料，尽管其理论比容量多在 100mAh/g以上，但在含钠 /钾离子的水溶液 中的有效可循环比容量低均在 100mAh/g 以下， 致使器件的能量密度偏低， 成为钠 / 钾离子储能技术推广的一个瓶颈， 亟需开发具有高容量的新型正极材料， 从而提高钠 /钾储能器件的能量密度。 发明内容 为了开发一种高容量、 低成本、 安全、 环保型水系储能器件， 本发明提供了一 种水系碱金属离子电化学储能器件， 包括正极、 负极、 隔膜和含碱金属离子的水相电 解液， 其特征在于， 该正极的活性材料为具有通式 A1+a(XmYnMni_m_n)02+b的含碱金属 多元过渡金属氧化物， 其中 A选自 Li、 Na和 K中的一种或多种； X， Y选自 M、 Co、 Al、 Cr、 V、 Ti和 Fe中的一种； 0 <m+n<l ; 0≤a， b<l， 在含钠或钾盐的水相电 解液中，所述正极的活性材料的多元过渡金属氧化物的晶体结构含有层状结构， 并且 所述正极以大于 100 mAh/g的有效比容量可逆循环。 在本发明的水系碱金属离子储能器件中，所述负极的活性材料可以选自活性炭、 石墨烯、碳纳米管、碳纤维和介孔碳中的一种或多种， 这些材料均是靠大的表面积进 行非法拉第双电层电子吸附过程， 与正极组成混合电容电池。也可以选自能够在水相 电解液中进行含有法拉第电子转移过程的可逆氧化还原反应的材料。此类材料包括碱 金属离子能够可逆嵌入和脱嵌的氧化物， 磷酸盐材料。 也包括在水相中可以进行可 逆的溶解和沉积反应的金属或合金材料。 上述在水相电解液中可进行含有法拉第电 子转移过程的可逆氧化还原反应的负极材料的可逆氧化还原反应电位不能低于该水 相电解液的析氢电位，以避免由于析氢反应这一不可逆电化学反应的发生所导致的器 件充放电库仑效率的下降。 在本发明的水系碱金属离子储能器件中， 所述正极材料的碱金属多元过渡金属 氧化物的晶体结构包含有层状结构。 该含碱金属多元过渡金属氧化物选自 LiNio.33Coo.33Mno.33O2、 LiNio.4Coo.2Mno.4O2、 LiNio.5Coo.2Mno.3O2、 LiNio.5Mno.5O2、 NaNio.33Coo.33Mno.33O2、 NaNio.4Coo.2Mno.4O2、 NaNio.5Coo.2Mno.3O2、 NaNio.5Mno.5O2、 KNio.33Coo.33Mno.33O2 KNio.5Coo.2Mno.3O2 KNio.4Coo.2Mno.4O2 KNio.5Mno.5O2中的一 种或几种的混合物， 或上述过渡金属氧化物的金属或非金属元素掺杂的材料。掺杂金 属包含 Li、 Mg、 Al、 Cu、 Cr、 Mg、 Zr、 Fe、 Mo中的一种或多种。 掺杂的非金属包 含？、 Si、 B中的一种或多种。 在本发明的水系碱金属离子储能器件中， 所述水相电解液包含但不局限于硫酸 钠、 硝酸钠、 卤化钠、 碳酸钠、 磷酸钠、 醋酸钠、 氢氧化钠、 高氯酸钠、 硫酸钾、 硝 酸钾、 卤化钾、 碳酸钾、 磷酸钾、 醋酸钾、 氢氧化钾、 高氯酸钾中的一种或多种混合 液。 电解液浓度为 0.5 - lO mol丄 pH值 在 3-12之间。 为了解决现有的室温水系碱金属离子电池正极材料能量密度低， 性能表现不佳 的问题，本发明提供了一种含碱金属的多元过渡金属氧化物正极材料。本发明的含碱 金属的多元过渡金属氧化物具有通式
Figure imgf000005_0001
其中 A选自 Li、 Na 和 K中的一种或多种； X和 Υ选自 ^^、0、 1、0\ ¥、1 和？6中的一种； 0 <m+n<l ; 0≤a， b<l。 具体地， 所述含碱金属多元过渡金属氧化物选自 LiM 33Co 33MnQ.3302、 LiNio.4Coo.2Mno.4O2、 LiNio.5Coo.2Mno.3O2、 LiNio.5Mno.5O2、 NaNio.33Coo.33Mno.33O2、 NaNio.4Coo.2Mno.4O2、 NaNio.5Coo.2Mno.3O2、 NaNio.5Mno.5O2、 KNio.33Coo.33Mno.33O2、 KNio.5Coo.2Mno.3O2 > KNio.4Coo.2Mno.4O2 > ΚΜ0.5Μη 5Ο2中的一种或几种。 所述正极材 料还需加入 1% - 10%的导电剂 （石墨、 炭黑、 乙炔黑等） 来提高材料导电性， 同时 还需加入 1% - 10%的粘结剂 （聚四氟乙烯、 聚偏氟乙烯等） 来制成均匀、 具有粘性 的混合材料， 再将该混合材料通过压力或导电胶固定在集电极上。集电极包含有不锈 钢、 镍、 钛、 石墨纤维布等。 所述含碱金属的多元过渡金属氧化物正极材料形貌为类球形， 其特征在于类球 形的颗粒是由纳米结构的一次颗粒团聚而形成的二次颗粒。其中纳米级的一次颗粒的 平均粒径小于 500纳米， 类球形二次颗粒的平均粒径在 1微米到 20微米的范围内。 所述含碱金属的多元过渡金属氧化物正极材料的前驱体是通过共沉淀的合成方 法制备的。 这种合成方法的最大特点是便于产业化。 与其相比， 溶胶凝胶法， 水热法 和微波法等尽管近年来在实验室规模的合成中被广泛用来合成纳米材料，但由于存在 原材料成本高， 工艺复杂， 合成条件苛刻， 合成周期长等问题， 不适合于大规模产业 化。 尤其不适合于成本被视为普及应用瓶颈的储能材料领域。 所述正极的活性材料为具有通式 A1+a(XmYnMni_m_n)02+b的含碱金属多元过渡金 属氧化物， 其中所述碱金属 A含有锂 （Li) ， 并且所述含锂正极的活性材料在所述 水系电化学储能器件组装前或组装后经过了化学或电化学的碱金属离子交换处理。含 锂正极的活性材料可以在器件组装前进行化学处理，是将活性材料放置于稀酸溶液中 进行浸泡， 从而使锂离子脱离。将含锂正极的活性材料进行电化学碱金属离子交换处 理， 是将活性材料置于含钠或钾盐溶液的电化学电池中，在一定电压范围内进行长时 间充放电循环， 使锂离子从正极材料的结构中脱出来， 并使钠或钾离子进入到正极材 料的结构中去， 从而实现钠或钾离子与锂离子之间的交换。 电化学碱金属离子交换处 理可以在器件组装前进行， 也可以在器件组装后再通过实施充放电活化来实现。 所述含碱金属的多元过渡金属氧化物正极材料在不同的水相钠盐或钾盐电解液 中均以大于 100 mAh/g的有效比容量进行可逆循环 。 解液里的应用， 可以降低成本和提高器件安全性能。 本发明将轻易实现碱金属 离子正极材料在水相碱金属离子电 附图说明 图 1是本发明实施例 1 中正极活性材料是 LiNi 5Co 2Mn 302-活性炭储能器件 的结构图。 图 2是本发明实施例 1 中 LiNi 5Co 2Mn 302-活性炭储能器件在硫酸钠水溶液 中的充放电曲线。 图 3是本发明实施例 1 中 LiNi 5Co 2Mn 302-活性炭储能器件在硫酸钾水溶液 中的充放电曲线。 图 4是本发明实施例 1 中 LiNi 5Co 2Mn 302-活性炭储能器件在硝酸钠水溶液 中的充放电曲线。 图 5是本发明实施例 1 中 LiNi 5Co 2Mn 302-活性炭储能器件在硝酸钠水溶液 中的循环性能曲线。 第 1到第 10循环为 0.1C充放电， 第 10循环之后为 1C充放电。 图 6是本发明实施例 1中 LiMQ.5Co 2Mn 302的 X射线粉末衍射 （XRD) 图。 图 7是本发明实施例 1中 LiM。.5Co。.2Mn 302的扫描电镜 （SEM) 图。 图 8是本发明实施例 2中 LiNi 33Co 33Mn 3302-活性炭储能器件在硫酸钠水溶 液中的充放电曲线。 图 9是本发明实施例 3中 LiNi 4Co 2Mn 402-活性炭储能器件在硫酸钾水溶液 中的充放电曲线。 具体实施方式 本发明将通过实施例进行更加详细的描述， 但本发明的保护范围并不受限于这 些实施例。 实施例 1 正极活性材料采用商业化的 LiMQ.5Co 2Mn 302。 正极材料按照 LiNio.5Coo.2Mno.3O2： 乙炔黑： PTFE粘结剂 = 80: 10: 10的质量比均匀混合， 烘干后将 混合物辊压或碾压到不锈钢网上， 然后制成 0.2mm厚的电极片。 负极材料采用商业 化的活性炭， 按照活性炭： 导电炭黑： PTFE粘结剂 = 80: 10: 10 的质量比均匀混合， 烘干后将混合物辊压或碾压到不锈钢网上， 然后制成 1 mm厚的电极片。 然后将正负 极电极按照规格裁切， 配对组装成 CR2032纽扣电池， 隔膜采用亲水处理过的 PP基 隔膜， 电解液分别为 lM Na2S04、 0.5M K2SO4、 2M NaN03水溶液， 电池结构如图 1 所示， 可逆循环充放电曲线分别如图 2、 3、 4所示， 在 0.2V-1.8V的电压区间， 充放 电电流为 0.1C，在 Na2S04、 K2S04、NaN03溶液中的可逆循环放电比容量分别是 120.5 mAh/g、 148.0 mAh/g、 120.9 mAh/g。 在 2M NaN03水溶液中的放电循环曲线如图 5 所示。 图 6是本发明实施例 1中 LiMQ.5Co 2Mn 302的 X射线粉末衍射 （XRD) 图。 图 7是本发明实施例 1中 LiMQ.5Co 2Mn 302的扫描电镜 （SEM) 图。 图 7显示该含 碱金属的多元过渡金属氧化物正极材料形貌为类球形，该类球形的颗粒是由纳米结构 的一次颗粒团聚而形成的二次颗粒， 其中纳米级的一次颗粒的平均粒径小于 500 纳 米， 类球形二次颗粒的平均粒径在 1微米到 20微米的范围内。 实施例 2 正极活性材料采用商业化的 LiMQ.33Co 33Mn 3302。 正极材料按照 LiNio.33Coo.33Mno.33O2： 乙炔黑： PTFE粘结剂 = 80: 10: 10的质量比均匀混合， 烘干后 将混合物辊压或碾压到不锈钢网上， 然后制成 0.2mm厚的电极片。 负极材料采用商 业化的活性炭，按照活性炭：导电炭黑： PTFE粘结剂 = 80: 10: 10 的质量比均匀混合， 烘干后将混合物辊压或碾压到不锈钢网上， 然后制成 l mm厚的电极片。 然后将正负 极电极按照规格裁切， 配对组装成 CR2032纽扣电池， 隔膜采用亲水处理过的 PP基 隔膜， 电解液为 1M的 Na2S04水溶液， 充放电曲线分别如图 8所示， 在 0.2V-1.8V 的电压区间， 充放电电流为 0.1C， 在 Na2S04水溶液中的可逆循环放电比容量分别是 122.1 mAh/g。 实施例 3 正极活性材料采用商业化的 LiM 4Co 2Mn 402。 正极材料按照 LiNio.4Coo.2Mno.4O2： 乙炔黑： PTFE粘结剂 = 80: 10: 10的质量比均匀混合， 烘干后将 混合物辊压或碾压到不锈钢网上， 然后制成 0.2mm厚的电极片。 负极材料采用商业 化的活性炭， 按照活性炭： 导电炭黑： PTFE粘结剂 = 80: 10: 10 的质量比均匀混合， 烘干后将混合物辊压或碾压到不锈钢网上， 然后制成 l mm厚的电极片。 然后将正负 极电极按照规格裁切， 配对组装成 CR2032纽扣电池， 隔膜采用亲水处理过的 PP基 隔膜， 电解液为 0.5M K2S04水溶液， 充放电曲线如图 9所示， 在 0.2V-1.8V的电压 区间， 放电电流为 0.1C的可逆循环放电比容量是 118.4 mAh/g。 以下的表 1 是不同的含碱金属多元过渡金属氧化物与一元过渡金属氧化物 (LiMn204和 NaQ.44Mn02 ) 在含 Na、 K金属盐的水溶液中的可逆循环放电比容量的 比较。 其中负极材料的活性材料为活性炭。 充放电电流 （倍率） 为 0.1C, 充放电电 压区间为 0.2-1.8 V。 表 1 可逆循环放电比容量 正极材料 电解液 With the development of science, technology, economy and society, energy and environmental issues have received more and more attention. The demand for energy continues to skyrocket. The shortage of fossil energy and environmental damage have turned the focus to renewable resources such as wind and solar. These renewable energy sources are greatly affected by weather and time periods, and are characterized by obvious instability, discontinuity and uncontrollability. It is necessary to develop and construct supporting electrical energy storage (storage energy) devices to ensure the continuity of power generation and power supply. stability. Therefore, large-scale energy storage technology is the key to vigorously develop renewable energy utilization and smart grids such as solar energy and wind energy. Among all the energy storage technologies, the battery can achieve efficient conversion between chemical energy and electrical energy, and is an optimal energy storage technology. Secondary rechargeable batteries are currently the most widely used energy storage method. Compared with other energy storage methods, electrochemical energy storage can adapt to different grid function needs, and it has advantages in integrated grid connection of wind power and photovoltaic. There are two major challenges to the promotion of rechargeable battery energy storage technology. The first is to develop battery systems with high voltage and high energy, and the second is to use low-cost, stable, environmentally friendly, long-life battery systems to ensure continuous supply of electrical energy from renewable and clean energy sources into the grid. . At present, the way for energy storage in large-scale power grids is based on traditional lead-acid batteries. Lead-acid batteries have low cost, but short life, and major materials such as lead and concentrated sulfuric acid cause serious pollution to the environment and require recycling. Therefore, there is an urgent need to find a new technology that can replace lead-acid batteries. In the past two decades, the development of lithium-ion battery technology has become more and more mature. Due to its high energy density and high output voltage, the application of lithium-ion batteries in different fields has also developed rapidly. However, since the lithium ion battery uses an organic solvent as the electrolyte, the manufacturing cost is high and there is a safety hazard that is flammable and explosive during use. Chinese Patent Licensing Publication No. CN1328818C discloses a hybrid water-based lithium ion battery. The working principle is: For the assembled battery, it must first be charged. During the charging process, lithium ions are removed from the positive electrode, and lithium ions are adsorbed to the negative electrode made of a material such as activated carbon through the electrolyte. During the discharge process, lithium ions are desorbed from the negative electrode, and lithium ions are inserted into the positive electrode through the electrolyte. The charge and discharge process involves only the transfer of lithium ions between the two electrodes. The positive electrode material of the hybrid water-based lithium ion battery is LiMn 2 0 4 , LiCo0 2 , LiCo 1/3 M 1/3 Mn 1/3 0 2 , LiMgo.2Mm.8O4 can reversibly intercalate lithium ion-extracting materials, and the negative electrode uses activated carbon, mesoporous carbon or carbon nanotubes having a specific surface area of 1000 m 2 /g or more. In addition, with the large-scale application of lithium-ion batteries, the demand for lithium will become larger and larger, and the price of lithium materials will become higher and higher due to the limited reserves in the earth's crust. In recent years, attention has been paid to replacing lithium with energy storage devices with cheaper alkali metals such as sodium, potassium or even alkaline earth metal magnesium. Sodium is abundant in the earth's crust, accounting for 2.74%. It is the sixth abundant element, widely distributed, and the price of raw materials containing sodium is low. And similar to the electrochemical properties of lithium, sodium-based batteries have gradually become lithium-ion batteries. Alternative option. In the early studies, sodium-based sodium-sulfur and Na/Cl 2 batteries, although having a relatively good energy density, used molten sodium as the negative electrode and the operating temperature was between 300 and 350 ° C, so it was necessary to use it. High thermal management system and special ceramic solid electrolyte. In addition, if the ceramic solid electrolyte breaks and forms a short circuit, the high-temperature liquid sodium and sulfur will be in direct contact, and a severe exothermic reaction will occur, resulting in a high temperature of 2000 ° C, which has a great safety hazard. Based on these backgrounds and reasons, room temperature sodium ion batteries have become a research hotspot. Chinese Patent Publication No. CN102027625A discloses an aqueous phase electrolyte electrochemical secondary energy storage device mainly composed of sodium ions, which comprises an anode electrode, a cathode electrode capable of reversibly deintercalating sodium cations, a separator and a sodium cation. An aqueous electrolyte, wherein the initial active cathode electrode material comprises an alkali metal-containing active cathode electrode material that deintercalates alkali metal ions during initial charging of the device. The active cathode electrode material may be aluminum-doped λ-Μη0 2 , NaMn0 2 (sodium manganite structure), Na 2 Mn 3 0 7 NaFeP0 4 F Na 0 . 44 MnO 2 . The anode electrode comprises porous activated carbon and the electrolyte comprises sodium sulfate. Chinese Patent Publication No. CN1723578A discloses a sodium ion battery comprising a positive electrode, a negative electrode and an electrolyte. The positive electrode includes an electrochemically active material capable of reversibly circulating sodium ions, and the negative electrode includes a carbon capable of intercalating sodium ions. The active material includes a sodium transition metal phosphate. The transition metal includes a transition metal selected from the group consisting of vanadium (v), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), nickel (M), and titanium (Ti), and mixtures thereof. Chinese Patent Publication No. CN101241802A discloses an asymmetric water-based sodium/potassium battery capacitor composed of a positive electrode, a negative electrode, a separator and an electrolyte. The active materials of the positive electrode are NaMn0 2 , NaCo0 2 , NaV 3 0 8 , NaVP0 4 F, and Na 2 VOP0 4 . The positive electrode active material is uniformly mixed with carbon black and a binder, coated on a nickel mesh current collector, dried and pressed into an electrode. The activated carbon is mixed with a conductive agent and a binder, uniformly coated on a nickel mesh current collector, dried and pressed into an electrode. A non-woven fabric was used as a separator, and sodium chloride or sodium sulfate was used as an electrolyte to assemble a battery. However, the above-mentioned phosphate positive electrode material having a spinel structure and a menorite structure or a core-shell structure, although having a theoretical specific capacity of more than 100 mAh/g, is contained in sodium/potassium ions. The effective recyclable specific capacity in the aqueous solution is below 100 mAh/g, resulting in low energy density of the device, which becomes a bottleneck for the promotion of sodium/potassium ion storage technology. It is urgent to develop a new positive electrode material with high capacity, thereby improving Energy density of sodium/potassium energy storage devices. SUMMARY OF THE INVENTION In order to develop a high-capacity, low-cost, safe, environmentally-friendly water-based energy storage device, the present invention provides an aqueous alkali metal ion electrochemical energy storage device comprising a positive electrode, a negative electrode, a separator, and an alkali metal ion-containing water. a phase electrolyte, characterized in that the active material of the positive electrode is an alkali metal-containing multicomponent transition metal oxide having the general formula A 1+a (X m Y n M ni _ m _ n ) 0 2+b , wherein A is selected From one or more of Li, Na and K; X, Y is selected from one of M, Co, Al, Cr, V, Ti and Fe; 0 <m+n<l; 0≤a, b <1, in the aqueous phase electrolyte containing sodium or potassium salt, the crystal structure of the multi-element transition metal oxide of the active material of the positive electrode contains a layered structure, and the positive electrode has an effective specific capacity of more than 100 mAh/g. Reversible cycle. In the aqueous alkali metal ion energy storage device of the present invention, the active material of the negative electrode may be selected from one or more of activated carbon, graphene, carbon nanotubes, carbon fibers, and mesoporous carbon, and these materials are all large. The surface area is subjected to an illegally drawn electric double layer electron adsorption process, and the positive electrode is composed of a hybrid capacitor battery. It may also be selected from materials capable of performing a reversible redox reaction containing a Faraday electron transfer process in an aqueous phase electrolyte. Such materials include oxides, phosphate materials that are capable of reversible intercalation and deintercalation of alkali metal ions. Also included are metal or alloy materials that can undergo reversible dissolution and deposition reactions in the aqueous phase. The reversible redox reaction potential of the negative electrode material capable of performing the reversible redox reaction of the Faraday electron transfer process in the aqueous phase electrolyte solution cannot be lower than the hydrogen evolution potential of the aqueous phase electrolyte to avoid irreversible electrochemistry due to hydrogen evolution reaction. The decrease in coulombic efficiency of charge and discharge of the device due to the occurrence of the reaction. In the aqueous alkali metal ion energy storage device of the present invention, the crystal structure of the alkali metal multi-element transition metal oxide of the positive electrode material contains a layered structure. The alkali metal-containing multicomponent transition metal oxide is selected from the group consisting of LiNio.33Coo.33Mno.33O2, LiNio.4Coo.2Mno.4O2, LiNio.5Coo.2Mno.3O2, LiNio.5Mno.5O2, NaNio.33Coo.33Mno.33O2, NaNio .4Coo.2Mno.4O2, NaNio.5Coo.2Mno.3O2, NaNio.5Mno.5O2, KNio.33Coo.33Mno.33O2 KNio.5Coo.2Mno.3O2 KNio.4Coo.2Mno.4O2 KNio.5Mno.5O2 a mixture of one or more of them, or a metal or non-metal element doped material of the above transition metal oxide. The doping metal contains one or more of Li, Mg, Al, Cu, Cr, Mg, Zr, Fe, and Mo. Doped non-metallic package Contain? One or more of Si, B, and B. In the aqueous alkali metal ion energy storage device of the present invention, the aqueous phase electrolyte solution includes, but is not limited to, sodium sulfate, sodium nitrate, sodium halide, sodium carbonate, sodium phosphate, sodium acetate, sodium hydroxide, sodium perchlorate. And a mixture of one or more of potassium sulfate, potassium nitrate, potassium halide, potassium carbonate, potassium phosphate, potassium acetate, potassium hydroxide, potassium perchlorate. The electrolyte concentration is 0.5 - 10 mol and the pH is between 3 and 12. In order to solve the problem that the current room temperature water-based alkali metal ion battery cathode material has low energy density and poor performance, the present invention provides an alkali metal-containing multi-element transition metal oxide cathode material. The alkali metal-containing multicomponent transition metal oxide of the present invention has a general formula
Figure imgf000005_0001
Wherein A is selected from one or more of Li, Na and K; X and Υ are selected from ^^, 0, 1, 0\ ¥, 1 and ? One of 6; 0 <m+n<l; 0≤a, b<l. Specifically, the alkali metal-containing multicomponent transition metal oxide is selected from the group consisting of LiM 33 Co 33 MnQ. 33 0 2 , LiNio. 4 Coo. 2 Mno. 4 O 2 , Li Nio. 5 Coo. 2 Mno. 3 O 2 , Li Nio. 5 Mno. 5 O 2 , NaNio. 33 Coo .33Mno.33O2, NaNio.4Coo.2Mno.4O2, NaNio.5Coo.2Mno.3O2, NaNio.5Mno.5O2, KNio.33Coo.33Mno.33O2, KNio.5Coo.2Mno.3O2 > KNio.4Coo.2Mno.4O2 > ΚΜ 0 .5Μη 5 Ο 2 one or more. The positive electrode material also needs to add 1% - 10% of conductive agent (graphite, carbon black, acetylene black, etc.) to improve the conductivity of the material, and also needs to add 1% - 10% of the binder (polytetrafluoroethylene, Polyvinylidene fluoride or the like is used to form a uniform, viscous mixed material, and the mixed material is fixed to the collector by pressure or conductive paste. The collector includes stainless steel, nickel, titanium, graphite fiber cloth, and the like. The alkali metal-containing multi-element transition metal oxide positive electrode material has a spheroidal shape, and is characterized in that the spheroidal particles are secondary particles formed by agglomeration of primary particles of nanostructures. Wherein the nano-sized primary particles have an average particle diameter of less than 500 nm, and the spheroidal secondary particles have an average particle diameter in the range of 1 micrometer to 20 micrometers. The precursor of the alkali metal-containing multicomponent transition metal oxide positive electrode material is prepared by a synthetic method of coprecipitation. The biggest feature of this synthesis method is that it is easy to industrialize. Compared with sol-gel method, hydrothermal method and microwave method, although it has been widely used in the synthesis of nano-materials in laboratory-scale synthesis in recent years, due to the high cost of raw materials, complicated process, harsh synthesis conditions, synthesis cycle Long issues are not suitable for large-scale industrialization. In particular, it is not suitable for the field of energy storage materials where cost is considered a common application bottleneck. The active material of the positive electrode is an alkali metal-containing multicomponent transition metal oxide having the general formula A 1+a (X m Y n M ni _ m _ n ) 0 2+b , wherein the alkali metal A contains lithium (Li And the active material containing the lithium positive electrode undergoes chemical or electrochemical alkali metal ion exchange treatment before or after assembly of the aqueous electrochemical energy storage device. The active material containing the lithium positive electrode can be chemically treated before the device is assembled, and the active material is placed in a dilute acid solution. Immersion is performed to detach lithium ions. The active material of the lithium-containing positive electrode is subjected to electrochemical alkali metal ion exchange treatment, and the active material is placed in an electrochemical cell containing a sodium or potassium salt solution, and a long-term charge and discharge cycle is performed in a certain voltage range to cause lithium ions to pass from The structure of the positive electrode material is removed, and sodium or potassium ions are introduced into the structure of the positive electrode material, thereby achieving exchange between sodium or potassium ions and lithium ions. The electrochemical alkali metal ion exchange treatment can be carried out before the device is assembled, or can be realized by performing charge and discharge activation after the device is assembled. The alkali metal-containing multicomponent transition metal oxide cathode material is reversibly circulated in an aqueous phase sodium or potassium salt electrolyte at an effective specific capacity of more than 100 mAh/g. The application in the solution can reduce costs and improve device safety. The present invention will readily realize an alkali metal ion positive electrode material in an aqueous phase alkali metal ion. FIG. 1 is a structural view of a positive electrode active material in the first embodiment of the present invention, which is a LiNi 5 Co 2 Mn 3 0 2 -activated carbon energy storage device. 2 is a graph showing charge and discharge curves of a LiNi 5 Co 2 Mn 3 0 2 -activated carbon energy storage device in an aqueous solution of sodium sulfate in Example 1 of the present invention. Fig. 3 is a graph showing charge and discharge curves of a LiNi 5 Co 2 Mn 3 0 2 -activated carbon energy storage device in an aqueous solution of potassium sulfate in Example 1 of the present invention. Fig. 4 is a graph showing charge and discharge curves of a LiNi 5 Co 2 Mn 3 0 2 -activated carbon energy storage device in an aqueous solution of sodium nitrate in Example 1 of the present invention. Fig. 5 is a graph showing the cycle performance of a LiNi 5 Co 2 Mn 3 0 2 -activated carbon energy storage device in an aqueous solution of sodium nitrate in Example 1 of the present invention. The first to tenth cycles were charged and discharged at 0.1 C, and after the tenth cycle, charged and discharged at 1 C. Figure 6 is an X-ray powder diffraction (XRD) pattern of LiM Q . 5 Co 2 Mn 3 0 2 in Example 1 of the present invention. Fig. 7 is a view showing LiM in the first embodiment of the present invention. . 5 Co. 2 Scanning electron microscopy (SEM) image of Mn 3 0 2 . Figure 8 is a graph showing the charge and discharge curves of a LiNi 33 Co 33 Mn 33 0 2 -activated carbon energy storage device in an aqueous solution of sodium sulfate in Example 2 of the present invention. Figure 9 is a diagram showing the LiNi 4 Co 2 Mn 4 0 2 -activated carbon energy storage device in the potassium sulfate aqueous solution in Example 3 of the present invention; The charge and discharge curve. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail by way of examples, but the scope of the invention is not limited thereto. Example 1 A positive electrode active material was commercialized LiM Q . 5 Co 2 Mn 3 0 2 . The positive electrode material was uniformly mixed according to the mass ratio of LiNio.5Coo.2Mno.3O2: acetylene black: PTFE binder = 80:10:10, and after drying, the mixture was rolled or rolled onto a stainless steel mesh, and then made 0.2 mm thick. Electrode piece. The negative electrode material is made of commercial activated carbon, and is uniformly mixed according to the mass ratio of activated carbon: conductive carbon black: PTFE binder = 80: 10: 10. After drying, the mixture is rolled or rolled onto a stainless steel mesh, and then made into 1 mm. Thick electrode pads. Then, the positive and negative electrodes are cut according to the specifications, and assembled into a CR2032 button battery. The separator is a hydrophilically treated PP-based separator, and the electrolytes are respectively 1M Na 2 S0 4 , 0.5MK 2 SO 4 , 2M NaN0 3 aqueous solution. The structure of the battery is shown in Figure 1. The reversible cycle charge and discharge curves are shown in Figures 2, 3 and 4, respectively. In the voltage range of 0.2V-1.8V, the charge and discharge current is 0.1C, in Na 2 S0 4 , K 2 S0 4. The specific capacity of reversible cyclic discharge in NaN0 3 solution is 120.5 mAh/g, 148.0 mAh/g, and 120.9 mAh/g, respectively. The discharge cycle curve in a 2M NaN0 3 aqueous solution is shown in Fig. 5. Figure 6 is an X-ray powder diffraction (XRD) pattern of LiM Q . 5 Co 2 Mn 3 0 2 in Example 1 of the present invention. Figure 7 is a scanning electron microscope (SEM) image of LiM Q . 5 Co 2 M n 3 0 2 in Example 1 of the present invention. Figure 7 shows that the alkali metal-containing multi-element transition metal oxide cathode material has a spheroidal shape, and the spherical particles are secondary particles formed by agglomeration of nanostructured primary particles, wherein the average particle of the nano-sized primary particles The diameter is less than 500 nm, and the average particle diameter of the spheroidal secondary particles is in the range of 1 micrometer to 20 micrometers. Example 2 A positive electrode active material was used as a commercial LiM Q . 33 Co 33 Mn 33 0 2 . The positive electrode material was uniformly mixed according to the mass ratio of LiNio.33Coo.33Mno.33O2: acetylene black: PTFE binder = 80:10:10, and after drying, the mixture was rolled or rolled onto a stainless steel mesh, and then made 0.2 mm thick. Electrode piece. The negative electrode material is made of commercial activated carbon, uniformly mixed according to the mass ratio of activated carbon: conductive carbon black: PTFE binder = 80: 10: 10, after drying, the mixture is rolled or rolled onto a stainless steel mesh, and then made into 1 mm. Thick electrode pads. Then, the positive and negative electrodes are cut according to the specifications, and assembled into a CR2032 button battery. The separator is a hydrophilically treated PP-based separator, and the electrolyte is a 1 M Na 2 S0 4 aqueous solution. The charge and discharge curves are respectively shown in FIG. 8 . At 0.2V-1.8V The voltage range, the charge and discharge current is 0.1 C, and the specific capacity of the reversible cyclic discharge in the Na 2 SO 4 aqueous solution is 122.1 mAh/g. Example 3 A positive electrode active material was commercialized LiM 4Co 2 Mn 4 0 2 . The positive electrode material was uniformly mixed according to the mass ratio of LiNio.4Coo.2Mno.4O2: acetylene black: PTFE binder = 80:10:10, and after drying, the mixture was rolled or rolled onto a stainless steel mesh, and then made 0.2 mm thick. Electrode piece. The negative electrode material is made of commercial activated carbon, and is uniformly mixed according to the mass ratio of activated carbon: conductive carbon black: PTFE binder = 80: 10: 10, after drying, the mixture is rolled or rolled onto a stainless steel mesh, and then made into 1 mm. Thick electrode pads. Then, the positive and negative electrodes are cut according to the specifications, and assembled into a CR2032 button battery. The separator is made of a hydrophilically treated PP-based separator, and the electrolyte is 0.5MK 2 S0 4 aqueous solution. The charge-discharge curve is shown in Fig. 9. In the voltage range of V-1.8V, the reversible cyclic discharge specific capacity with a discharge current of 0.1C is 118.4 mAh/g. Table 1 below shows the reversible cyclic discharge specific capacity of different alkali metal-containing transition metal oxides and mono-port transition metal oxides (LiMn 2 0 4 and Na Q .44Mn0 2 ) in an aqueous solution containing Na, K metal salts. Comparison. The active material of the negative electrode material is activated carbon. The charge and discharge current (magnification) is 0.1C, and the charge and discharge voltage range is 0.2-1.8 V. Table 1 Reversible cyclic discharge specific capacity positive electrode material electrolyte
(mAh/g)  (mAh/g)
LiNio.5Coo.2Mno.302 1 M Na2S04 120.5 LiNio.5Coo.2Mno.302 1 M Na 2 S0 4 120.5
LiNio.5Coo.2Mno.302 0.5 M K2S04 148.0 LiNio.5Coo.2Mno.302 0.5 MK 2 S0 4 148.0
LiNio.5Coo.2Mno.302 2 M NaN03 120.9 LiNio.5Coo.2Mno.302 2 M NaN0 3 120.9
LiNio.33Coo.33Mno.3302 1 M Na2S04 122.1 LiNio.33Coo.33Mno.3302 1 M Na 2 S0 4 122.1
LiNio.4Coo.2Mno.402 0.5 M K2S04 118.4 LiNio.4Coo.2Mno.402 0.5 MK 2 S0 4 118.4
LiMn204 1M Na2S04 76.3 LiMn 2 0 4 1M Na 2 S0 4 76.3
Na0.44MnO2 1M Na2S04 44.1 虽然已经以具体实施例的方式描述了本发明，但是对于本领域技术人员来说明 显的是，在不脱离所附权利要求书所限定的本发明的精神和范围的情况下，可以对本 发明进行各种变化和修改， 这些变化和修改同样包括在本发明的范围内。 Na 0 .44MnO 2 1M Na 2 S0 4 44.1 Although the present invention has been described in terms of the specific embodiments thereof, it is apparent to those skilled in the art that the present invention can be carried out without departing from the spirit and scope of the invention as defined by the appended claims. Various changes and modifications are also included in the scope of the present invention.

Claims

权 利 要 求 Rights request
1. 一种水系电化学储能器件， 包括正极、 负极、 隔膜和含碱金属电解质的 水相电解液，其特征在于，所述正极的活性材料为具有通式 A1+a(XmYnMni_m_n)02+b 的含碱金属多元过渡金属氧化物， 其中 A选自 Li、 Na和 K中的一种或多种； X， Y选自 Ni、 Co、 Al、 Cr、 V、 Ti和 Fe中的一种； 0 <m+n<l; 0≤a， b<l， 所 述正极的活性材料的含碱金属多元过渡金属氧化物的晶体结构含有层状结构，并 且所述正极以大于 100 mAh/g的有效比容量可逆循环，所述电解液为含钠或钾盐 的水溶液。 A water-based electrochemical energy storage device comprising a positive electrode, a negative electrode, a separator, and an aqueous phase electrolyte containing an alkali metal electrolyte, wherein the active material of the positive electrode has a general formula A 1+a (X m Y n M ni _ m _ n ) 0 2+b of an alkali metal-containing multicomponent transition metal oxide, wherein A is selected from one or more of Li, Na and K; X, Y is selected from Ni, Co, Al, One of Cr, V, Ti, and Fe; 0 <m+n<l; 0≤a, b<l, the crystal structure of the alkali metal-containing transition metal oxide of the active material of the positive electrode contains a layered structure And the positive electrode reversibly circulates at an effective specific capacity of more than 100 mAh/g, which is an aqueous solution containing sodium or potassium salt.
2. 根据权利要求 1 所述的水系电化学储能器件， 其特征在于， 所述含碱金 属多元过渡金属氧化物材料的形貌是具有纳米结构的一次颗粒聚集形成微米级 二次颗粒的类球形。 2. The aqueous electrochemical energy storage device according to claim 1, wherein the morphology of the alkali metal-containing transition metal oxide material is a class in which primary particles having a nanostructure are aggregated to form micron secondary particles. spherical.
3. 根据权利要求 1 所述的水系电化学储能器件， 其特征在于， 所述正极的 活性材料为具有通式 A1+a(XmYnMni_m_n)02+b的含碱金属多元过渡金属氧化物，其 中所述碱金属 A含有锂 （Li) ， 并且所述含锂正极的活性材料在所述水系电化 学储能器件组装前或组装后经过了化学或电化学的碱金属离子交换处理。 3. The aqueous electrochemical energy storage device according to claim 1, wherein the active material of the positive electrode has a general formula A 1+a (X m Y n M ni _ m _ n ) 0 2+b An alkali metal-containing multicomponent transition metal oxide, wherein the alkali metal A contains lithium (Li), and the active material of the lithium-containing positive electrode undergoes chemical or electrical treatment before or after assembly of the aqueous electrochemical energy storage device Chemical alkali metal ion exchange treatment.
4. 根据权利要求 1 所述的水系电化学储能器件， 其特征在于， 所述负极材 料至少包含一种能够在水相电解液中与钠离子或 /和钾离子进行可逆电化学反应 的材料。 4. The aqueous electrochemical energy storage device according to claim 1, wherein the anode material comprises at least one material capable of reversible electrochemical reaction with sodium ions and/or potassium ions in an aqueous phase electrolyte. .
5. 根据权利要求 1 所述的水系电化学储能器件， 其特征在于， 所述负极材 料至少包含一种能够在水相电解液中进行钠离子或 /和钾离子嵌入和脱嵌的材 料。 The aqueous electrochemical energy storage device according to claim 1, wherein the negative electrode material comprises at least one material capable of intercalating and deintercalating sodium ions or/and potassium ions in an aqueous phase electrolyte.
6. 根据权利要求 1 所述的水系电化学储能器件， 其特征在于， 所述负极的 活性材料选自活性炭、石墨烯、碳纳米管、碳纤维和介孔碳中的一种或多种材料。 The aqueous electrochemical energy storage device according to claim 1, wherein the active material of the negative electrode is one or more selected from the group consisting of activated carbon, graphene, carbon nanotubes, carbon fibers, and mesoporous carbon. .
7. 根据权利要求 1 所述的水系电化学储能器件， 其特征在于， 所述水相电 解液包含有钠盐、 钾盐电解质中的一种或多种。 7. The aqueous electrochemical energy storage device according to claim 1, wherein the aqueous phase electrolyte solution comprises one or more of a sodium salt and a potassium salt electrolyte.
8. 根据权利要求 1 所述的水系电化学储能器件， 其特征在于， 所述水相电 解液选自硫酸钠、 硝酸钠、 卤化钠、 碳酸钠、 磷酸钠、 醋酸钠、 氢氧化钠、 高氯 酸钠、 硫酸钾、 硝酸钾、 卤化钾、 碳酸钾、 磷酸钾、 醋酸钾、 氢氧化钾、 高氯酸 钾中的一种或多种。 8. The aqueous electrochemical energy storage device according to claim 1, wherein the aqueous phase electrolyte is selected from the group consisting of sodium sulfate, sodium nitrate, sodium halide, sodium carbonate, sodium phosphate, sodium acetate, sodium hydroxide, One or more of sodium perchlorate, potassium sulfate, potassium nitrate, potassium halide, potassium carbonate, potassium phosphate, potassium acetate, potassium hydroxide, potassium perchlorate.
9. 根据权利要求 1 所述的水系电化学储能器件， 其特征在于， 所述含碱金 属多元过渡金属氧化物选自 LiM0.33Co0.33Mn0.33O2、 LiNio.4Coo.2Mno.4O2、 LiNio.5Coo.2Mno.3O2 LiNio.5Mno.5O2 > NaNio.33Coo.33Mno.33O2 NaNio.4Coo.2Mno.4O2 NaNio.5Coo.2Mno.3O2 NaNio.5Mno.5O2 > KNio.33Coo.33Mno.33O2 KNio.5Coo.2Mno.3O2 > KNio.4Coo.2Mno.4O2 > ΚΜο.5Μηο.502中的一种或几种的混合物， 或上述过渡金属氧 化物的金属、 非金属元素掺杂的材料。 9. The aqueous electrochemical energy storage device according to claim 1, wherein the alkali metal-containing multicomponent transition metal oxide is selected from the group consisting of LiM 0 . 33 Co 0 .33Mn 0 . 33 O 2 , LiNio. 4 Coo. 2Mno.4O2, LiNio.5Coo.2Mno.3O2 LiNio.5Mno.5O2 > NaNio.33Coo.33Mno.33O2 NaNio.4Coo.2Mno.4O2 NaNio.5Coo.2Mno.3O2 NaNio.5Mno.5O2 > KNio.33Coo.33Mno. 33O2 KNio.5Coo.2Mno.3O2 > KNio.4Coo.2Mno.4O2 > ΚΜο. 5 Μηο. a mixture of one or more of 5 0 2 , or a metal or non-metal element doped with the above transition metal oxide material.
PCT/CN2013/086064 2013-03-27 2013-10-28 Water-based alkali metal ion energy storage device WO2014153957A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2013101034782A CN103219551A (en) 2013-03-27 2013-03-27 Water-system alkali metal ion power storage device
CN201310103478.2 2013-03-27

Publications (1)

Publication Number Publication Date
WO2014153957A1 true WO2014153957A1 (en) 2014-10-02

Family

ID=48817153

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/086064 WO2014153957A1 (en) 2013-03-27 2013-10-28 Water-based alkali metal ion energy storage device

Country Status (2)

Country Link
CN (1) CN103219551A (en)
WO (1) WO2014153957A1 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103219551A (en) * 2013-03-27 2013-07-24 恩力能源科技（南通）有限公司 Water-system alkali metal ion power storage device
CN103259009B (en) * 2013-04-18 2019-06-14 恩力能源科技有限公司 A kind of water-system alkali metal ion electrochemical energy storing device
CN104347894A (en) * 2013-08-02 2015-02-11 中国人民解放军63971部队 A sedimentary type aqueous lithium ion battery
CN104064824A (en) * 2014-06-10 2014-09-24 恩力能源科技（南通）有限公司 Water system rechargeable battery
WO2016085726A1 (en) * 2014-11-26 2016-06-02 3M Innovative Properties Company Anode materials for sodium-ion batteries and methods of making same
US10811684B2 (en) * 2015-12-07 2020-10-20 National Institute Of Advanced Industrial Science And Technology Potassium compound and positive electrode active material for potassium ion secondary batteries containing same
CN106057477B (en) * 2016-07-22 2019-11-29 清华大学 A kind of water system Na ion chargeable capacitor batteries and preparation method thereof
CN108630458B (en) * 2017-03-20 2020-11-10 北京大学深圳研究生院 Aqueous electrolyte and application thereof
CN106935909A (en) * 2017-05-08 2017-07-07 山东大学 A kind of flame retardant type kalium ion battery electrolyte and preparation method thereof
CN107871903A (en) * 2017-05-15 2018-04-03 中国科学院金属研究所 A kind of electric capacity negative pole/insertion positive-type water system sodium ion capacitor batteries
CN107634215B (en) * 2017-08-28 2020-11-03 山东大学 Novel potassium ion battery positive electrode material K0.27MnO2Preparation method of (1)
CN108390026B (en) * 2018-01-22 2020-07-14 李慧 Cage type positive electrode material and preparation method and application thereof
CN109103457B (en) * 2018-08-09 2021-06-25 吉林大学 Nanoporous gold/potassium vanadate aqueous potassium ion micro-battery and preparation method and application thereof
CN109524248A (en) * 2018-12-06 2019-03-26 中国科学院兰州化学物理研究所 A kind of construction method of zinc ion mixed capacitor
CN110993944B (en) * 2019-11-08 2023-07-25 宁波锋成先进能源材料研究院 Water-based ion battery and application thereof
CN113437285B (en) * 2020-03-23 2022-08-16 中国科学院化学研究所 Positive electrode material of potassium ion secondary battery and preparation method and application thereof
CN115050935B (en) * 2022-06-09 2024-07-23 广州大学 Layered high-nickel ternary lithium ion battery positive electrode material, preparation method and application

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1674347A (en) * 2005-04-21 2005-09-28 复旦大学 Mixed aquo-lithium ion battery
CN101154745A (en) * 2007-09-20 2008-04-02 复旦大学 Hydrographical rechargeable lithium or sodium ion battery
CN101241802A (en) * 2008-03-13 2008-08-13 复旦大学 A non symmetric water natrium/kalium ion battery capacitor
CN102055029A (en) * 2010-12-17 2011-05-11 复旦大学 High-safety aqueous and organic mixed lithium ion battery
CN103219551A (en) * 2013-03-27 2013-07-24 恩力能源科技（南通）有限公司 Water-system alkali metal ion power storage device

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5405091B2 (en) * 2008-12-01 2014-02-05 三洋電機株式会社 Non-aqueous electrolyte battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1674347A (en) * 2005-04-21 2005-09-28 复旦大学 Mixed aquo-lithium ion battery
CN101154745A (en) * 2007-09-20 2008-04-02 复旦大学 Hydrographical rechargeable lithium or sodium ion battery
CN101241802A (en) * 2008-03-13 2008-08-13 复旦大学 A non symmetric water natrium/kalium ion battery capacitor
CN102055029A (en) * 2010-12-17 2011-05-11 复旦大学 High-safety aqueous and organic mixed lithium ion battery
CN103219551A (en) * 2013-03-27 2013-07-24 恩力能源科技（南通）有限公司 Water-system alkali metal ion power storage device

Also Published As

Publication number Publication date
CN103219551A (en) 2013-07-24

Similar Documents

Publication Publication Date Title
WO2014153957A1 (en) Water-based alkali metal ion energy storage device
Wu et al. The electrochemical performance of aqueous rechargeable battery of Zn/Na0. 44MnO2 based on hybrid electrolyte
CN107221716B (en) Rechargeable aqueous zinc ion battery
JP5462445B2 (en) Lithium ion secondary battery
CN102891299B (en) High-rate lithium ion battery cathode material and preparation method and application thereof
CN107482182B (en) Carbon-coated ion-doped manganese phosphate lithium electrode material and preparation method thereof
CN102891309B (en) Preparation method of spherical lithium-enriched anode material with gradient concentration
WO2015021789A1 (en) High-magnification anode material of aqueous alkali metal electrochemical cell, and preparation method thereof
WO2014169717A1 (en) Electrochemical energy storage device of aqueous alkali metal ions
WO2015021788A1 (en) Aqueous alkaline electrochemical energy-storage device
KR20140039022A (en) Battery
CN102651484A (en) Energy storage device combining with characteristics of lithium ion battery and super-capacitor
CN103545123A (en) Hybrid energy storage device with zinc ion battery and supercapacitor
Wu et al. Synthesis and electrochemical performance of SnO2–Fe2O3 composite as an anode material for Na-ion and Li-ion batteries
Liu et al. 120 Years of nickel-based cathodes for alkaline batteries
CN104167540A (en) Negative electrode active material and preparation method thereof and lithium ion battery
Zhang et al. Ni-Doped magnesium manganese oxide as a cathode and its application in aqueous magnesium-ion batteries with high rate performance
CN103178252B (en) A kind of anode material for lithium-ion batteries and preparation method thereof
CN106935830B (en) lithium ion battery composite positive electrode material and preparation method and application thereof
CN112803023B (en) Lanthanum-zirconium-codoped high-nickel ternary cathode material and preparation method and application thereof
Yao et al. Hydrothemal synthesis of porous NiO nanosheets and application as anode material for lithium ion batteries
CN110336035B (en) Tin dioxide/aluminum oxide doped carbon composite material and preparation method thereof
CN103198935A (en) Preparation method of graphene sheet modified spinel type lithium manganate or alpha type manganese dioxide electrode
CN111994896A (en) Carbon composite negative electrode material, preparation method thereof and lithium ion battery
CN106549152A (en) Ternary layered positive electrode of a kind of sodium-ion battery and preparation method thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13880218

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13880218

Country of ref document: EP

Kind code of ref document: A1