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WO2016034143A1 - 一种二次电池负极材料 - Google Patents

一种二次电池负极材料 Download PDF

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Publication number
WO2016034143A1
WO2016034143A1 PCT/CN2015/088921 CN2015088921W WO2016034143A1 WO 2016034143 A1 WO2016034143 A1 WO 2016034143A1 CN 2015088921 W CN2015088921 W CN 2015088921W WO 2016034143 A1 WO2016034143 A1 WO 2016034143A1
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negative electrode
battery
secondary battery
group
electrode material
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French (fr)
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颜竞
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Nanjing Jingyan New Energy Technology Co Ltd
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Nanjing Jingyan New Energy Technology Co Ltd
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Priority to US15/505,154 priority Critical patent/US10270085B2/en
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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
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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 invention belongs to the field of electrochemical energy storage, and in particular relates to a secondary battery anode material.
  • the technology described herein combines the advantages of a water-based lithium battery with the aforementioned lithium-zinc battery, using a chelating/adsorbing group to "fix" the metal ion to redox it in situ in the negative electrode material, apparently, If the material is combined with a lithium-embedded positive electrode such as LiMn 2 O 4 , the macroscopic performance and battery design will be similar to that of the water-based lithium ion battery, and the chelate/adsorption type negative electrode can ensure the stability of the material and solve the Zn2+ solution.
  • the present invention is directed to providing a secondary battery negative electrode material.
  • the negative electrode material proposed by the invention has an unprecedented charge and discharge mechanism, and the metal/metal ion electrode has been widely studied in the past, for example, lithium metal as a negative electrode in a lithium battery and zinc as a negative electrode in a zinc-bromine battery.
  • the electrode has an almost infinite lifetime in principle, but due to the dendritic problem of metal/metal ions during charging, such electrodes, although having very good electrochemical properties, are difficult to find in the battery industry.
  • the invention provides a secondary battery anode material, which can completely overcome the dendrite problem of metal/metal ions during charging.
  • a secondary battery anode material mainly composed of a skeleton, a chelating/adsorbing group, and a "fixed" active material, a divalent or polyvalent metal ion, the skeleton being an organic polymer, and the skeleton passing a chemical bond that immobilizes the chelating/adsorbing group on a backbone, the chelating/adsorbing group being a group comprising atoms of O, N, P, etc. having an outer electron having a lone pair of electrons, said hydrazine
  • the binding/adsorbing group may form an ionic bond or a coordinate bond with the divalent or polyvalent metal ion of the active material.
  • the secondary battery negative electrode material skeleton provided by the present invention does not participate in the reaction itself, but serves as a carrier.
  • the chelate/adsorbing group is chemically bonded to the carrier backbone, and the chelate/adsorbing group itself does not participate in the electrochemical redox reaction, but is linked to the active metal ion by a chelate bond or a chemisorption bond.
  • the metal ion as the active material is immobilized on the chelating group in the form of chelation or chemisorption, and the electron can be reduced to a lower-valent state or a zero-valent state in situ.
  • the organic polymer may be polystyrene, polyvinyl chloride, polymethacrylic acid, polyacrylic acid, polyethylene or polypropylene.
  • the chelating/adsorbing group may be an iminodiacetic acid group, a carboxylic acid group or a phosphoric acid group.
  • the active material divalent or polyvalent metal ion may be a metal ion having an electrochemical redox potential of -1.2 V (relative to a hydrogen standard electrode potential) in an aqueous solution.
  • the active material divalent or polyvalent metal ion may be Cu 2+ , Fe 2+ , Fe 3+ , Pb 2+ , Zn 2+ , Mn 2+ , Ni 2+ or Transition metal ions such as V 3+ .
  • the secondary battery negative electrode material of the present invention can be paired with a lithium intercalation compound such as LiMn 2 O 4 or LiFePO 4 or a sodium ion intercalation compound positive electrode material such as NaMnxOy to form a secondary battery excellent in performance, and thus the secondary battery negative electrode material of the present invention Has a very far-reaching significance.
  • a lithium intercalation compound such as LiMn 2 O 4 or LiFePO 4
  • a sodium ion intercalation compound positive electrode material such as NaMnxOy
  • FIG. 1 is a schematic view showing the basic working principle of the iminodiacetic acid group-zinc anode material of the present invention, showing a typical skeleton-iminodiacetic acid chelating group-zinc ion type compound charging and discharging process working diagram, The chelated zinc ions are reduced to metallic zinc during charging. Since the anode material of the present invention can be charged and discharged in an aqueous solution, it can also be combined with many other types of cathode materials to form a rechargeable secondary battery.
  • FIG. 2 is a schematic diagram of the working principle of the battery according to Embodiment 1 of the present invention.
  • FIG. 3 is a schematic diagram of a working principle of a battery discharged according to Embodiment 1 of the present invention.
  • FIG. 4 is a structural view of a battery according to an embodiment of the present invention.
  • Example 5 is a graph showing the first voltage-time charge and discharge curves of a LiMn 2 O 4 /R-iminodiacetic acid group-Zn battery according to Example 1 of the present invention.
  • Figure 6 is a graph showing the cycle performance of a LiMn 2 O 4 /R-iminodiacetic acid group-Zn battery according to Example 1 of the present invention.
  • Fig. 7 is a structural view of an electrode material of the present invention having a polymer of acrylic acid (top)/methacrylic acid (lower image) as a skeleton, a chelate/adsorbing group being a carboxyl group, and an active metal ion being a zinc ion.
  • Fig. 10 is a graph showing charge and discharge curves of the battery of Example 4.
  • Figure 11 is a schematic view of the negative electrode in Example 5, wherein the active material is zinc, the chelate adsorption group is an aminophosphonic acid group, the upper graph shows the state of unchelated zinc ions, and the lower graph shows the state of having chelated zinc ions.
  • FIG. 12 is a graph showing a charge-discharge voltage-time curve of a LiMn 2 O 4 /R-aminophosphonic acid group-Zn battery of Example 5.
  • the divalent or polyvalent metal obtains electrons which are reduced to a lower valence state, or a zero valent metal state.
  • the discharge process (see Fig. 3) is the reverse process of charging, and the metal as the active material is again changed to the chelate/adsorption state.
  • the reaction of the positive electrode during charging is:
  • the reaction of the negative electrode is:
  • LiMn 2 O 4 is a positive electrode active material, and the electrolyte is a 1 mol/L Li 2 SO 4 battery, which is charged in LiMn 2 O 4 .
  • the Li + ions are removed from the spinel lattice while a trivalent manganese in the crystal lattice is oxidized to tetravalent and an electron is output.
  • LiMn 2 O 4 lithium ions coming out since the shape becomes Li 1-x Mn 2 O 4, while chelated zinc ions RC-Zn material is reduced and deposited to obtain an electron in an external circuit from the anode material.
  • the positive electrode reacts to LiMn 2 O 4 -xe- ⁇ Li + +Li 1-x Mn 2 O 4 during charging, and the negative electrode reacts with RC-Zn 2+ +2e- ⁇ RC-Zn.
  • the discharge process is the reverse process of the charging process, that is, the oxidation of the zero-valent zinc of the negative electrode and re-conversion into chelated zinc ions, and the positive electrode obtains electrons and is inserted into Li 1-x Mn 2 O 4 with lithium ions.
  • the general formula of the material should be strictly as described in the general formula of the spinel structure compound provided by the present invention.
  • the chemical formula expression of the material is complicated by the means of doping, inclusion modification, etc., so the LiMn 2 O 4 described in the present invention, in terms of its technical essence, should be broadly included after various modifications.
  • the chemical formula of a material such as LiFePO 4 described in the present invention should also include a material of a general formula which has been modified to conform to a layered structure compound, a spinel structure compound or an olivine structure compound.
  • the negative electrode material provided by the present invention solves the dendrite problem that is difficult to solve when the metal/metal ion electrode is used as a battery negative electrode.
  • the negative electrode material provided by the invention is environmentally friendly and inexpensive.
  • the battery produced by the negative electrode material provided by the present invention is excellent in performance.
  • the unit of mass by volume in the present invention is well known to those skilled in the art and, for example, refers to the mass of the solute in a 100 ml solution.
  • positive electrode sheet LiMn 2 O 4 is used as positive electrode active material, according to positive electrode active material 90%: conductive carbon black 6%: adhesive SBR (styrene-butadiene rubber latex) 2%: thickener CMC (carboxyl Base cellulose sodium) 2% ratio, first mix CMC with a certain amount of water, then add active material and conductive carbon black, stir for 2 hours, and finally add SBR for 10 minutes to obtain a positive electrode slurry.
  • the positive electrode current collector was a 150 mesh SUS304 stainless steel mesh, and the positive electrode slurry was uniformly coated on the positive electrode current collector, and cut into a size of 10 mm ⁇ 10 mm and a weight of 50 mg. Dry at 120 ° C for 12 hours to form a positive electrode sheet.
  • negative electrode active material 1Kg of commercially available iminodiacetic acid chelating resin (PUROLITE S930, a crosslinked polystyrene-based skeleton, an iminodiacetic acid group as a reactive group, and a special large
  • the precursor is mixed with a saturated zinc sulfate solution, wherein the mass ratio of the precursor to zinc sulfate is 1:3, the pH value is controlled between 2-6, and the mixture is stirred for 3 hours, filtered, washed and dried to obtain the second time of the present invention.
  • Battery anode material is controlled between 2-6.
  • the negative electrode active material is mixed with tin dioxide, conductive carbon black and zinc powder by a ball mill at a mass ratio of 7:0.5:0.5:2, and pressed into a sheet shape, the size is 10 mm ⁇ 10 mm, and the mass is 200 mg.
  • the battery anode current collector is a zinc foil with a thickness of 0.05 mm.
  • the electrolytic solution was an aqueous solution containing a concentration of 1 mol/L of lithium sulfate, and the pH was adjusted to 4.
  • the positive electrode sheet and the negative electrode sheet were assembled into a battery, and the separator was separated by a separator, and the separator was a nonwoven fabric separator.
  • the battery positive electrode active material has a mass of about 45 mg, a negative electrode active material of about 140 mg, and a theoretical capacity of about 5 mAh.
  • the battery structure is as shown in FIG. A 1 ml electrolyte was injected and the charge and discharge tests were performed after standing for 12 hours. The charge and discharge voltage range is 1.4-2.1V. The battery charge-discharge voltage-time curve is shown in Figure 5. The battery demonstrates excellent cycle performance, as shown in Figure 6.
  • the synthetic product is similar to the skeleton-iminodiacetic acid.
  • the material of zinc should be regarded as the same technology as this embodiment.
  • a battery was fabricated in the same manner as in Example 1, except that the negative electrode active material was prepared as follows:
  • the positive electrode of the battery was the lithium manganate pole piece described in Example 1, the positive and negative electrode areas were the same, the positive and negative electrode mass ratio was 1:1, and the electrolyte solution was a neutral lithium sulfate solution having a pH of 7.
  • the chelating/adsorbing group of the material is a carboxyl group
  • the two carboxyl groups attached to the carrier form an ionic bond with the zinc ion and fix the zinc ion.
  • the charge and discharge performance is similar to that described in Example 1 in which the iminodiacetic acid group is a chelating group, but the quality of the negative electrode material is reduced, thereby increasing the energy density of the battery.
  • a battery was fabricated in the same manner as in Example 1, except that the negative electrode active material was prepared as follows:
  • the battery positive electrode used the lithium manganate pole piece described in Example 1, the positive and negative electrode pieces were the same size, the active material mass ratio was 1:1, and the electrolyte solution was a neutral lithium sulfate solution of pH 7.
  • the structure of the material prepared by the method is shown in Fig. 7.
  • the chelating/adsorbing group of the material is a carboxyl group, and the two carboxyl groups attached to the carrier form an ionic bond with the zinc ion and fix the zinc ion, charge and discharge.
  • the properties are similar to those described in Example 1 in which the iminodiacetic acid group is a chelating group, but the quality of the negative electrode material is reduced.
  • the positive electrode was mixed in such a manner that lithium manganate: conductive carbon black: PTFE had a mass ratio of 8:1:1, and was pressed into a sheet having a size of 60 mm ⁇ 60 mm, and the mass was 3 g.
  • the positive current collector was a graphite sheet having a thickness of 500 ⁇ m.
  • the preparation method of the negative electrode is as follows:
  • polyacrylic acid weak acid adsorption resin (DIAION WK10, a methacrylic type weakly acidic cation exchange resin adsorption group structure shown in Figure 7) was pulverized to a screen of 800 mesh, 400 g of lead acetate dissolved in 1 L of water Pour the resin powder, mix the solution for 10 hours, filter and wash, then mix the resin with carbon black conductive agent, PTFE powder at a mass ratio of 6.5:3:0.5, and compact it into 60mm ⁇ 60mm (thickness about 0.7mm), quality It is a 4g pole piece attached to a 100um thick lead foil.
  • DIAION WK10 a methacrylic type weakly acidic cation exchange resin adsorption group structure shown in Figure 7
  • the electrolyte is 1mol/L lithium acetate solution
  • the positive electrode tab and the negative electrode tab were separated by 70 mm X 70 mm filter paper, and 4 ml of electrolyte was injected to form a battery.
  • the structure is shown in FIG. 4 .
  • the battery was subjected to 50 mA constant current charge and discharge to obtain a charge and discharge curve as shown in Fig. 10, and the battery exhibited very good reversibility.
  • the positive electrode was mixed in such a manner that lithium manganate: conductive carbon black: PTFE had a mass ratio of 8:1:1, and was pressed into a sheet having a size of 60 mm ⁇ 60 mm, and the mass was 3 g.
  • the positive current collector was a graphite sheet having a thickness of 500 ⁇ m.
  • the preparation method of the negative electrode is as follows:
  • the electrolyte is 1mol/L lithium sulfate solution
  • the positive electrode tab and the negative electrode tab were separated by 70 mm X 70 mm filter paper, and 10 ml of electrolyte was injected to form a battery.
  • the structure is shown in FIG. 4 .
  • the battery was subjected to 50 mA constant current charge and discharge to obtain a charge and discharge curve as shown in Fig. 12, and the battery exhibited very good reversibility.
  • positive electrode sheet LiMn 2 O 4 is used as positive electrode active material, according to positive electrode active material 90%: conductive carbon black 6%: adhesive SBR (styrene-butadiene rubber latex) 2%: thickener CMC (carboxyl Base cellulose sodium) 2% ratio, first mix CMC with a certain amount of water, then add active material and conductive carbon black, stir for 2 hours, and finally add SBR for 10 minutes to obtain a positive electrode slurry.
  • the positive electrode current collector was a 150 mesh SUS304 stainless steel mesh, and the positive electrode slurry was uniformly coated on the positive electrode current collector to have a coating density of about 500 g/m 2 . Dry at 120 ° C for 12 hours to form a positive electrode sheet.
  • chloromethylated crosslinked polystyrene spheres chlorine spheres
  • ammonia were aminated at a temperature of 50 ° C for 12 hours using dimethylformamide (DMF) as solvent.
  • the amount of ammonia was The chlorine content of the chloromethylated crosslinked polystyrene sphere is 4 times.
  • the mother liquor is filtered off and the solid product is washed with ethanol.
  • the solid substance is added in 1 part of the solid content while cooling in a cold water bath, and stirring is continued, and 3 is slowly added. Part by weight of chloroacetic acid, followed by continuous addition of sodium hydroxide solution and maintaining the pH of the solution above 10.
  • the reaction temperature was less than 70 ° C for 20 hours.
  • the solid matter is filtered, washed and dried for use.
  • the dried reactant was placed in a 20% aqueous sodium hydroxide solution for 5 hours, filtered, and washed until the washing liquid was neutral to obtain a negative electrode material precursor.
  • the precursor is mixed with a saturated zinc sulfate solution, wherein the mass ratio of the precursor to zinc sulfate is 1:3, and the mixing and stirring time is 3 hours, and the secondary battery negative electrode material of the present invention is obtained by filtration, washing and drying.
  • the negative electrode active material is mixed with tin dioxide, conductive carbon black and zinc powder in a ratio of 7:0.5:0.5:2, and a certain proportion of deionized water is added to form a black slurry.
  • the coating density was 1200 g/m 2 on the battery anode current collector.
  • the battery negative current collector is a copper tin-plated foil, wherein the copper foil has a thickness of 0.02 mm and the tin plating layer has a thickness of 0.005 mm to 0.01 mm.
  • the electrolytic solution was an aqueous solution containing a concentration of 1 mol/L of lithium sulfate, and the pH was adjusted to 4.
  • the positive electrode sheet and the negative electrode sheet were assembled into a battery, and the separator was separated by a separator, and the separator was a nonwoven fabric separator.
  • the battery positive electrode active material has a mass of about 50 mg, a negative electrode active material of about 150 mg, and a theoretical capacity of about 5 mAh.
  • the battery structure is as shown in FIG.
  • the electrolyte was injected and the charging and discharging tests were carried out after standing for 12 hours.
  • the charge and discharge voltage range is 1.4-2.1V.
  • the battery first charge and discharge voltage-time curve is as shown in Fig. 5 of the first embodiment.
  • the battery exhibited excellent cycle performance as shown in Figure 6 of Example 1.
  • the negative electrode material of the present invention is not a single material but a combination of materials.
  • the microstructure of the material obtained by the combination of different skeletons and chelating/adsorbing functional groups is different, but the principle is similar to that of the battery, and it can be seen that the skeleton or the chelating/adsorbing group is simply replaced, or as described in Examples 1, 3 and 4. It is within the scope of the invention to make obvious modifications to the chelating group.

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Abstract

一种二次电池负极材料，所述材料包括骨架、螯合/吸附基团和活性物质。所述骨架不参与电化学反应，只是为螯合/吸附基团提供载体；所述螯合/吸附基团含有N、S、P、O等外层电子具有孤对电子的原子，并能够与2价、多价金属形成螯合或者化学吸附键(图中以亚氨基二乙酸鳌合基团作为代表)；所述活性物质为可还原为更低价态的2价或多价金属离子。充电时作为活性物质的金属离子被还原成更低价态或者金属单质状态，放电时则可逆地生成金属离子并与螯合/吸附基团形成螯合或者化学吸附键。该负极材料能够与许多正极材料搭配组成电池。该电池凭借廉价和可靠性，非常有望在电动汽车、大型储能项目上得到应用。

Description

一种二次电池负极材料 技术领域
本发明属于电化学储能领域，具体涉及一种二次电池负极材料。
背景技术
当前对于储能技术的需求远远超过人类历史上的任何时候。无论是新能源汽车，还是未来的风能，太阳能电站配套，抑或是城市智能电网削峰填谷等都需要数量巨大的可靠储能技术。
而目前商业化的电池技术主要是古老的，对环境破坏巨大的铅酸电池，新兴的锂离子电池在便携设备上获得了巨大的成功，但在大型化的动力或者储能领域则由于价格，安全等因素被制约。因此发展一种安全，廉价的可充电电池是非常紧迫的课题。
1994年加拿大Jeff Dahn研究小组的Wu Li在SCIENCE杂志发表了一篇以VO2为负极材料LiMn2O4为正极材料和以水溶液作为电解液的文献，该技术开创了水系锂离子电池的先河，但由于锂嵌入型负极材料稳定性问题长期得不到根本解决，经过近20年发展，该类电池仍然无法获得实际应用。
2009年，中国研究人员颜竞(Jing Yan)在专利201010154104.X以及2011年在journal of power sources 2012.05.063中报道了一种以LiMn2O4为正极材料，水溶液作为电解液，同时水溶液中的锌离子作为负极活性物质的电池体系(锂-锌电池)，该体系彻底解决了水系锂离子电池的负极稳定性问题，但基本机理的改变也使得该电池不再能被称为水系锂离子电池，而成了一种全新的电池体系，暂且称为颜氏电池。该电池由于使用传统的Zn/Zn2+电极，不可避免地面临着锌枝晶的问题，使电池的设计非常困难。
本文所述技术综合了水系锂电池与前述锂-锌电池电池的优点，使用螯合/吸附基团将金属离子进行“固定”，使其在负极材料原位进行氧化还原，表观上看，如果将该材料与LiMn2O4这类锂嵌入型正极组成电池，其宏观表现与电池设计将与水系锂离子电池类似，而螯合/吸附型负极又保证了材料的稳定性， 解决了Zn2+/Zn电极充放电过程中锌枝晶的问题。
该材料的工作机理是前所未有的，将带来电池技术的一项革命。
发明内容
本发明旨在提供一种二次电池负极材料。
本发明所提出的负极材料具有一种前所未有的充放电机理，金属/金属离子电极已经在过去被广泛研究，例如锂电池中以金属锂作为负极，锌溴电池中以锌作为负极等，该类电极原理上拥有几乎无限的寿命，但由于金属/金属离子在充电过程中枝晶问题，该类电极尽管具有非常优良的电化学性能，却很难在电池工业中获得广泛的应用。
本发明提供了一种二次电池负极材料，可以彻底克服金属/金属离子在充电过程中枝晶问题。
本发明的技术方案如下：
一种二次电池负极材料，它主要由骨架、鳌合/吸附基团和被“固定”的活性物质二价或多价金属离子组成，所述的骨架是有机聚合物，所述的骨架通过化学键将所述的鳌合/吸附基团固定在骨架上，所述的鳌合/吸附基团是包含外层电子具有孤对电子的O、N、P等原子的基团，所述的鳌合/吸附基团可以和所述的活性物质二价或多价金属离子形成离子键或者配位键。
本发明提供的二次电池负极材料骨架本身不参与反应，只是作为一个载体。而鳌合/吸附基团则与载体骨架以化学键连接，螯合/吸附基团本身也不参与电化学氧化还原反应，但是与活性物质金属离子以螯合键或者化学吸附键相连。作为活性物质的金属离子，以螯合或者化学吸附的形式固定在螯合基团上，可以在原位得到电子被还原成更低价态或零价状态。
上述的二次电池负极材料，所述的有机聚合物可以是聚苯乙烯、聚氯乙烯、聚甲基丙烯酸、聚丙烯酸、聚乙烯或聚丙烯。
上述的二次电池负极材料，所述的螯合/吸附基团可以是亚氨基二乙酸基团，羧酸基团或氨基磷酸基团。
上述的二次电池负极材料，所述的活性物质二价或多价金属离子可以是在水溶液中，电化学氧化还原电位在-1.2V(相对氢标准电极电位)以上的金属离子。
上述的二次电池负极材料，所述的活性物质二价或多价金属离子可以是Cu2+、Fe2+、Fe3+、Pb2+、Zn2+、Mn2+、Ni2+或V3+等过渡金属离子。
本发明的二次电池负极材料能够与LiMn2O4、LiFePO4等锂嵌入化合物,或者NaMnxOy等钠离子脱嵌化合物正极材料配对组成性能优良的二次电池，因此本发明的二次电池负极材料具有非常深远的意义。
附图说明
图1为本发明所述亚氨基二乙酸基团-锌负极材料的基本工作原理示意图，显示了一种典型的骨架-亚氨基二乙酸螯合基团-锌离子型化合物充放电过程工作示意图，充电过程中螯合的锌离子被还原成金属锌。由于本发明所述的负极材料能够在水溶液中完成充放电，因此也可以与很多其他类型的正极材料搭配而组成可充电二次电池。
图2为本发明实施例1提供的电池充电时工作原理示意图。
图3为本发明实施例1提供的电池放电时工作原理示意图。
图4为本发明实施例的电池结构图。
图5为本发明实施例1的LiMn2O4/R-亚氨基二乙酸基团-Zn电池首次电压－时间充放电曲线图。
图6为本发明实施例1的LiMn2O4/R-亚氨基二乙酸基团-Zn电池循环性能图。
图7为本发明的以丙烯酸(上图)/甲基丙烯酸(下图)型聚合物为骨架，螯合/吸附基团为羧基，活性物质金属离子为锌离子为的电极材料结构图。
图8为实施例3的LiMn2O4/R-羧基基团-Zn电池的充放电电压－时间曲线图
图9为实施例3的LiMn2O4/R-羧基基团-Zn电池的循环性能图。
图10为实施例4的电池的充放电曲线图。
图11为实施例5中负极示意图，其中活性物质为锌，螯合吸附基团为氨基膦酸基团，上图为未螯合锌离子的状态，下图为已经螯合锌离子的状态
图12为实施例5的的LiMn2O4/R-氨基膦酸基团-Zn电池的充放电电压－时间曲线图
具体实施方式
本发明的负极材料，在充电过程中(可参见附图2)，该2价或多价金属获得电子被还原为更低价态，或者0价金属态。放电过程(可参见附图3)，为充电的逆过程，作为活性物质的金属重新变为螯合/吸附态。
比如，如果以锂离子嵌入型化合物Li(HOST)作为电池正极材料，以Zn2+离子作为本报道所述的金属活性物质，则在充电时正极的反应为：
Li(HOST)－e-→Li++(HOST)－
负极的反应为：
R-C-Zn2++2e-→R-C-Zn，(其中R表示骨架，C表示鳌合/吸附基团)
以LiMn2O4/R-C-Zn电池为例(可参见附图4)，LiMn2O4为正极活性物质、电解液为1mol/L的Li2SO4组成电池，充电时LiMn2O4中的Li+离子从尖晶石晶格中脱出，同时晶格内一个三价锰被氧化为四价，同时输出一个电子。LiMn2O4由于脱出锂离子而变成Li1-xMn2O4的形态，同时，R-C-Zn材料中的螯合态锌离子从外电路得到电子被还原并沉积在负极材料中。充电时正极反应为LiMn2O4－xe-→Li++Li1-xMn2O4，负极反应为R-C-Zn2++2e-→R-C-Zn。放电过程为充电过程的逆过程，即负极0价锌的氧化并重新转化为螯合态锌离子，正极获得了电子并伴随锂离子插入Li1-xMn2O4中。说明：目前锂电池工业中，几乎所有正极材料都经过掺杂，包袱等改性处理。例如LiMn2O4已经不能够代表目前广泛使用的“锰酸锂”的通式。该材料的通式严格来说应该以本发明提供的尖晶石结构的化合物的通式中所述为准。但掺杂，包袱改性等手段造成材料的化学通式表达复杂，因此本发明中所述的LiMn2O4，就其技术实质来说，应该是广泛地包括了经过各种改性，符合本发明提供的尖晶石结构的化合物通式所述的正极材料。而本发明中所述的LiFePO4等材料的化学式，也应该包括经过各种改性的，通式符合层状结构化合物、尖晶石结构化合物或橄榄石结构化合物的通式的材料。
本发明的主要优点在于：
1、本发明提供的负极材料解决了金属/金属离子电极作为电池负极时难以解决的枝晶问题。
2、本发明提供的负极材料环保，廉价。
3、以本发明提供的负极材料所制作的电池性能优良。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。除非另外说明，否则所有的百分数、比率、比例、或份数按质量计。
本发明中的质量体积百分比中的单位是本领域技术人员所熟知的，例如是指在100毫升的溶液中溶质的质量。
除非另行定义，说明书中所使用的所有专业与科学用语与本领域熟练人员所熟悉的意义相同。此外，任何与所记载内容相似或均等的方法及材料皆可应用于本发明方法中。说明书中所述的较佳实施方法与材料仅作示范之用，实施例1,2,3和4能够向本领域熟练技术人员证明本发明原理的正确性。
实施例1二次电池的制备
1、正极片的制备：以LiMn2O4为正极活性物质，按照正极活性物质90％：导电碳黑6％：粘接剂SBR(丁苯橡胶乳)2％：增稠剂CMC(羧甲基纤维素钠)2％的比例，先将CMC与一定量水混合均匀，再加入活性物质及导电炭黑，搅拌2小时，最后加入SBR搅拌10分钟得到正极浆料。正极集流体为150目SUS304不锈钢网，将正极浆料均匀涂覆在正极集流体上，切成尺寸为10mmX10mm，重量为50mg。120℃烘干12小时成正极片。
2、负极活性材料的制备：将市售亚氨基二乙酸螯合树脂1Kg(PUROLITE S930，一种以交联聚苯乙烯为基础骨架、以亚胺基二乙酸基为活性基团、具有特殊大孔结构的螯合树脂)放置于10L 20％质量分数的氢氧化钠溶液中浸泡24h，随后用去离子水洗涤至pH＝6-9。100℃烘干，球磨机粉碎至过400目，即得到负极材料前驱体。
前驱体与饱和硫酸锌溶液混合，其中前驱体与硫酸锌的质量比例为1:3，控制pH值于2-6之间，混合搅拌3小时，过滤并洗涤烘干即得到本发明的二次电池负极材料。
3.二次电池的制备：将负极活性物质与二氧化锡，导电炭黑，锌粉以质量比7:0.5:0.5:2的比例混合球磨，压制成片状，尺寸为10mmX10mm,质量200mg。 电池负极集流体为锌箔，厚度0.05mm。电解液为含有浓度为1mol/L硫酸锂的水溶液，调节pH值为4，将正极片，负极片组装成电池，中间以隔膜隔开，隔膜为无纺布隔膜。
该电池正极活性物质质量约45mg,负极活性物质约140mg，理论容量约5mAh。电池结构如附图4所示。注入1ml电解液，静止12小时后即可进行充电和放电测试。充放电电压区间为1.4-2.1V。电池首次充放电电压-时间曲线如图5所示。电池展示了优秀的循环性能，如图6所示。
考虑到同样使用亚胺基二乙酸基为活性基团的同一大类不同牌号的螯合树脂骨架会稍微有所差异，但在本实施例中，凡是合成产物类似于骨架-亚氨基二乙酸-锌的材料，都应视为与本实施例同等技术。
实施例2
与实施例1相同的方式制造电池，所不同的是负极活性材料制备方法如下：
取100克聚丙烯酸钠(分子量10000)置于1L去离子水中，将400克硫酸锌溶解于1L水中，随后倒入上述聚丙烯酸钠和水的混合液中，溶液混合10小时，洗涤并过滤，然后将其与炭黑导电剂以至量比8:1:1混合，压制成极片，单位面积质量与正极相同，负极贴在锌箔集流体上。
电池正极使用实施例1里所述的锰酸锂极片，正负极面积相同，正负极质量比为1:1，电解液为pH＝7的中性硫酸锂溶液。
该方法所制得的材料结构图如图7(上)所示，该材料的鳌合/吸附基团是羧基，连接在载体上的两个羧基与锌离子形成离子键并将锌离子固定住，充放电性能与以亚氨基二乙酸基为鳌合基团的实施例1中所述材料类似，但负极材料质量有所减轻，从而提高电池能量密度。
电池得到的充放电曲线如图10所示
实施例3
与实施例1相同的方式制造电池，所不同的是负极活性材料制备方法如下：
取100克聚丙烯酸系弱酸吸附树脂(DIAION WK10，一种甲基丙烯酸型弱酸性阳离子交换树脂，结构如图7下所示)粉碎至过400目筛网，将400克硫酸锌溶解于1L水中，倒入上述树脂粉末，溶液混合10小时，洗涤并过滤，然后将其与炭黑导电剂，粘接剂PTFE粉末以至量比8:1:1混合，压制成片状， 贴在锌箔集流体上。
电池正极使用实施例1里所述的锰酸锂极片，正负极极片大小相同，活性物质质量比为1:1，电解液为pH7的中性硫酸锂溶液。
该方法所制得的材料结构图如图7所示，该材料的鳌合/吸附基团是羧基，连接在载体上的两个羧基与锌离子形成离子键并将锌离子固定住，充放电性能与以亚氨基二乙酸基为鳌合基团的实施例1中所述材料类似，但负极材料质量有所减轻。
电池得到的充放电曲线如图8所示，循环次数－容量图如图9所示
实施例4
正极按照锰酸锂:导电炭黑:PTFE的质量比为8:1:1的方式混合，压成尺寸60mmX60mm的片，质量为3g。正极集流体为厚度500微米的石墨片。
负极制备方法如下：
取100克聚丙烯酸系弱酸吸附树脂(DIAION WK10，一种甲基丙烯酸型弱酸性阳离子交换树脂吸附基团结构式如图7下所示)粉碎至过800目筛网，400克醋酸铅溶解于1L水中，倒入树脂粉末，溶液混合10小时，过滤并洗涤，然后所述树脂与炭黑导电剂，PTFE粉末以质量比6.5:3:0.5混合，碾压成60mmX60mm(厚度约为0.7mm)，质量为4g的极片，贴附在100um厚的铅箔上。
电解液为1mol/L醋酸锂溶液
正极极片与负极极片之间用70mmX70mm滤纸隔开，注入4ml电解液，做成电池，结构如图4所示。
对电池进行50mA恒流充放电，得到充放电曲线如图10所示，电池展现了非常良好的可逆性。
实施例5
正极按照锰酸锂:导电炭黑:PTFE的质量比为8:1:1的方式混合，压成尺寸60mmX60mm的片，质量为3g。正极集流体为厚度500微米的石墨片。
负极制备方法如下：
取100克氨基膦酸螯合树脂(BayerTP260，吸附基团结构式如图11所示，上图为未吸附态，下图为吸附锌离子的状态)粉碎至过800目筛网，400克醋酸锌溶解于1L水中，倒入树脂粉末，溶液混合10小时，过滤并洗涤，然后 所述树脂与炭黑导电剂，PTFE粉末以质量比6.5:3:0.5混合，碾压成60mmX60mm(厚度约为0.7mm)，质量为9g的极片，贴附在100um厚的锌箔上。
电解液为1mol/L硫酸锂溶液
正极极片与负极极片之间用70mmX70mm滤纸隔开，注入10ml电解液，做成电池，结构如图4所示。
对电池进行50mA恒流充放电，得到充放电曲线如图12所示，电池展现了非常良好的可逆性。
实施例6二次电池的制备
1、正极片的制备：以LiMn2O4为正极活性物质，按照正极活性物质90％：导电碳黑6％：粘接剂SBR(丁苯橡胶乳)2％：增稠剂CMC(羧甲基纤维素钠)2％的比例，先将CMC与一定量水混合均匀，再加入活性物质及导电炭黑，搅拌2小时，最后加入SBR搅拌10分钟得到正极浆料。正极集流体为150目SUS304不锈钢网，将正极浆料均匀涂覆在正极集流体上，涂覆密度约500g/m2。120℃烘干12小时成正极片。
2、负极活性材料的制备：以二甲基甲酰胺(DMF)为溶剂，将氯甲基化交联聚苯乙烯球体(氯球)和氨在温度50℃下胺化12小时，氨用量为氯甲基化交联聚苯乙烯球体氯含量质量的4倍，反应后过滤抽去母液并以乙醇洗涤固体产物，在冷水浴冷却下加入上述固形物质量1份并维持搅拌，缓缓加入3份质量份氯乙酸，随后持续加入氢氧化钠溶液并保持溶液pH值高于10。反应温度小于70℃，时间20小时。反应完毕将固形物过滤，洗涤烘干备用。将烘干的反应物置于20％氢氧化钠水溶液中5小时，过滤，洗涤至洗液中性，即得到负极材料前驱体。
前驱体与饱和硫酸锌溶液混合，其中前驱体与硫酸锌的质量比例为1:3，混合搅拌时间3小时，过滤并洗涤烘干即得到本发明的二次电池负极材料。
3.二次电池的制备：将负极活性物质与二氧化锡，导电炭黑，锌粉以7:0.5:0.5:2的比例混合球磨，加入一定比例的去离子水形成黑色泥浆状，涂覆于电池负极集流体上，涂覆密度为1200g/m2。电池负极集流体为铜镀锡箔，其中铜箔厚度0.02mm，镀锡层厚度0.005mm-0.01mm。电解液为含有浓度为1mol/L硫酸锂的水溶液，调节pH值为4，将正极片，负极片组装成电池，中间以隔膜隔开，隔膜为无纺布隔膜。
该电池正极活性物质质量约50mg,负极活性物质约150mg，理论容量约5mAh。电池结构如附图4所示。注入电解液，静止12小时后即可进行充电和放电测试。充放电电压区间为1.4-2.1V。电池首次充放电电压-时间曲线如实施例1图5所示。电池展示了优秀的循环性能，如实施例1图6所示。
由此可见，本发明所述的负极材料并非单一一种材料，而是一类组合材料。不同的骨架和螯合/吸附官能团配合得到的材料微观结构有所区别，但原理与电池放电性能类似，可见单纯更换骨架或者鳌合/吸附基团，或者对实施例1、3和4所述鳌合基团进行显而易见的修改，都属于本发明的范畴。

Claims (6)

  1. 一种二次电池负极材料，其特征是：它主要由骨架、鳌合/吸附基团和被“固定”的活性物质二价或多价金属离子组成，所述的骨架是有机聚合物，所述的骨架通过化学键将所述的鳌合/吸附基团固定在骨架上，所述的鳌合/吸附基团是含有外层电子具有孤对电子的O、N、P原子的基团，所述的鳌合/吸附基团和所述的活性物质二价或多价金属离子形成离子键或者配位键。
  2. 根据权利要求1所述的二次电池负极材料，其特征是：所述的有机聚合物是聚苯乙烯、聚氯乙烯、聚甲基丙烯酸、聚丙烯酸、聚乙烯或聚丙烯；
  3. 根据权利要求1所述的二次电池负极材料，所述的螯合/吸附基团是亚氨基二乙酸基团、羧酸基团或氨基磷酸基团。
  4. 根据权利要求1所述的二次电池负极材料，其特征是：所述的活性物质二价或多价金属离子是在水溶液中，电化学氧化还原电位在-1.2V以上的金属离子。
  5. 根据权利要求4所述的二次电池负极材料，所述的活性物质二价或多价金属离子是Cu2+、Fe2+、Fe3+、Pb2+、Zn2+、Mn2+、Ni2+或V3+过渡金属离子。
  6. 权利要求1所述的二次电池负极材料在制备二次电池中的应用。
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