WO2017201758A1 - 金属离子/螯合树脂-锂金属复合氧化物电池及其负极 - Google Patents

金属离子/螯合树脂-锂金属复合氧化物电池及其负极 Download PDF

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WO2017201758A1
WO2017201758A1 PCT/CN2016/083758 CN2016083758W WO2017201758A1 WO 2017201758 A1 WO2017201758 A1 WO 2017201758A1 CN 2016083758 W CN2016083758 W CN 2016083758W WO 2017201758 A1 WO2017201758 A1 WO 2017201758A1
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negative electrode
metal
battery
resin
metal ion
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French (fr)
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苏义松
郭永胜
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Ningde Amperex Technology Ltd
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Ningde Amperex Technology Ltd
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the present invention belongs to the field of batteries, and more particularly to a metal ion/chelating resin-lithium metal composite oxide battery having a desired cycle performance and a negative electrode thereof.
  • Metal ion/chelating resin batteries have been widely used in recent years because of their environmental, low cost and safety advantages.
  • the metal ion/chelating resin negative electrode contains a large amount of chelating resin particles, and the chelating resin particles adsorb metal ions in the electrolytic solution to lower the concentration of metal ions.
  • metal ions are converted to inactive compounds during the cycle, including oxides, hydroxides, and the like. As the metal ions are lost, the capacity of the battery is continuously reduced as the cycle progresses, resulting in deterioration of the cycle performance of the battery.
  • the present invention provides a metal ion/chelating resin battery negative electrode comprising a negative electrode current collector and a negative electrode material layer distributed on the negative electrode current collector, the negative electrode material layer including a skeleton and a chelate fixed on the skeleton a combined/adsorbing group and a metal ion formed on the chelate/adsorbing group by an ionic bond or a coordinate bond, wherein the negative electrode current collector and the negative electrode material layer, the negative electrode material layer, and the negative electrode material layer are away from the negative electrode At least one of the sides of the current collector is provided with a corresponding metal element that replenishes the active metal ions.
  • the metal element is selected from the group consisting of zinc, magnesium, lead, chromium, tin, cadmium, iron, copper, vanadium or nickel.
  • the metal element is at least one selected from the group consisting of metal foil, metal powder, metal foam or metal mesh.
  • the skeleton is selected from the group consisting of polystyrene resin, polyvinyl chloride resin, polymethacrylic resin, polyacrylic resin, polyethylene resin or polypropylene resin. At least one.
  • the chelating/adsorbing group contains a phosphoric acid group, an imidodiacetic acid group or a carboxylic acid group.
  • the present invention also provides a metal ion/chelating resin-lithium metal composite oxide battery comprising a positive electrode containing a lithium metal composite oxide, a negative electrode containing a metal ion, and a positive electrode and a negative electrode.
  • the lithium-containing metal composite oxide is selected from the group consisting of lithium manganate, lithium iron phosphate, lithium cobaltate, lithium nickelate, and nickel cobalt manganese. At least one of lithium acid.
  • the present invention also provides a method for preparing a metal ion/chelating resin battery anode, which comprises the following steps:
  • the anode membrane is disposed on the anode current collector to form a metal ion/chelating resin battery anode, wherein at least between the anode current collector and the anode material layer, the anode material layer, and the anode material layer away from the anode current collector side A metal element that replenishes active metal ions is provided in one place.
  • the metal element is selected from the group consisting of zinc, magnesium, lead, chromium, tin, cadmium, iron, copper, vanadium or nickel.
  • the metal element is at least one selected from the group consisting of metal foil, metal powder, metal foam or metal mesh.
  • the skeleton is selected from the group consisting of polystyrene resin, polyvinyl chloride resin, polymethacrylic resin, polyacrylic resin, polyethylene resin or polypropylene. At least one of the resins.
  • the chelating/adsorbing group contains at least one of a phosphoric acid group, an imidodiacetic acid group or a carboxylic acid group.
  • the metal ion/chelating resin-lithium metal composite oxide battery of the present invention and the negative electrode thereof have the following advantages: after the active metal ion is converted into an inactive metal compound, the metal element is slowly converted into an active metal. The ions replenish the continuously lost active metal ions, thereby significantly increasing the cycle life of the metal ion/chelating resin-lithium metal composite oxide battery, keeping the capacity of the battery not decreasing as the cycle progresses.
  • FIG. 1A and FIG. 1B are schematic diagrams showing the structure of a battery of a metal ion/chelating resin-lithium manganate battery according to Embodiment 1 of the present invention and a battery structure of a metal ion/chelating resin-lithium manganate battery according to Embodiment 4 of the present invention.
  • Example 2 is a graph showing the charge and discharge performance of the zinc ion/chelating resin-lithium manganate battery of Example 1 and Example 4 of the present invention, wherein the voltage range is 1.5-2.3V.
  • Preparation of positive electrode 70 wt% of positive electrode material lithium manganate powder (300 mesh), 20 wt% of conductive agent conductive carbon SP001 and 10 wt% of binder PTFE are uniformly mixed in deionized water to prepare a positive electrode slurry; The slurry was pressed into a film having a film thickness of 0.6 mm and an area weight of 500 g/m 2 ; the film was cut into a 3 ⁇ 5 cm 2 positive electrode film; and the positive electrode film was removed in an oven at 110-130° C. Solvent; a positive electrode film and a 50 micron thick positive electrode current collector stainless steel foil were formed into a battery positive electrode.
  • the styrene resin containing the iminodiethylzinc group (Xi'an blue deep resin) was dispersed in absolute ethanol and ball milled in a ball mill for 4 hours, the ball mill rotation speed was 550 rpm; the ball-milled resin was placed Drying in an oven at 80 ° C, using a sieve to separate resin powder of less than 200 mesh; 80 wt% of sieved negative electrode material resin powder, 10 wt% of conductive agent conductive carbon SP001, 7 wt% of binder PTFE, 3 wt % thickener CMC is uniformly mixed in ethanol to prepare a negative electrode slurry; the negative electrode slurry is pressed into a film having a film thickness of 1 mm and an area weight of 300 g/m 2 ; the film is cut into 3.1 ⁇ 5.1 cm.
  • a negative electrode membrane of 2 removing the solvent remaining in the negative electrode film in an oven at 70-120 ° C; placing a zinc foil between the negative electrode film and a 20 ⁇ m thick negative electrode current collector stainless steel foil to form a battery negative electrode; compacting battery
  • the negative electrode makes the current collector, the zinc foil and the negative electrode material close to each other, reduces the influence of residual air on the battery, increases the contact between the negative electrode material and the negative electrode current collector, and reduces the resistance of the negative electrode.
  • the structure of the negative electrode of the battery is shown in Fig. 1(A). Shown.
  • the battery positive electrode, the battery negative electrode, and the separator were assembled into a battery, and 1 ml of the electrolyte was injected and sealed in a vacuum atmosphere to prepare a zinc ion/chelating resin-lithium manganate battery.
  • Battery test conditions The assembled battery was subjected to constant current charge and discharge at a rate of 1 C in a voltage range of 1.5 V to 2.3 V, and its capacity, specific capacity, coulombic efficiency, and number of cycles were calculated.
  • the zinc ion/chelating resin-lithium manganate battery is substantially the same as the zinc ion/chelating resin-lithium manganate battery of the first embodiment of the present invention, except that the amine is contained in the preparation of the battery negative electrode.
  • Phosphorus The zinc styrene resin (Xi'an Blue Deep Resin) replaces the styrene resin (Xi'an Blue Deep Resin) containing an iminodiethylzinc group.
  • the zinc ion/chelating resin-lithium manganate battery is substantially the same as the zinc ion/chelating resin-lithium manganate battery of the first embodiment of the present invention, except that the acetic acid is contained in the preparation of the battery negative electrode.
  • a zinc styrene resin (Xi'an Blue Deep Resin) replaces a styrene resin (Xi'an Blue Deep Resin) containing an iminodiethylzinc group.
  • Preparation of positive electrode 70 wt% of positive electrode material lithium manganate powder (300 mesh), 20 wt% of conductive agent conductive carbon SP001 and 10 wt% of binder PTFE are uniformly mixed in deionized water to prepare a positive electrode slurry; The slurry was pressed into a film having a film thickness of 0.6 mm and an area weight of 500 g/m 2 ; the film was cut into a 3 ⁇ 5 cm 2 positive electrode film; and the positive electrode film was removed in an oven at 110-130° C. Solvent; a positive electrode film and a 50 micron thick positive electrode current collector stainless steel foil were formed into a battery positive electrode.
  • the styrene resin containing the iminodiethylzinc group (Xi'an blue deep resin) was dispersed in absolute ethanol and ball milled in a ball mill for 4 hours, the ball mill rotation speed was 550 rpm; the ball-milled resin was placed Drying in an oven at 80 ° C, using a sieve to separate particles below 200 mesh; 70 wt% of sieved negative electrode material resin powder, 10 wt% of conductive agent conductive carbon SP001, 10 wt% of 200 mesh zinc powder, 7 wt%
  • the binder PVDF, 3wt% thickener CMC is uniformly mixed in ethanol to prepare a negative electrode slurry; the negative electrode slurry is pressed into a membrane having a membrane thickness of 0.6 mm and an area weight of 400 g/m 2 ; The film is cut into a negative film of 3.1 ⁇ 5.1 cm 2 ; the solvent remaining in the negative film is removed in an oven at 70-120° C.
  • the battery positive electrode, the battery negative electrode, and the separator are assembled into a battery, and 1 ml of electricity is injected.
  • the solution was sealed and sealed under vacuum to prepare a zinc ion/chelating resin-lithium manganate battery.
  • the zinc ion/chelating resin-lithium manganate battery is substantially the same as the zinc ion/chelating resin-lithium manganate battery of the fourth embodiment of the present invention, except that the amine is contained in the preparation of the battery negative electrode.
  • the styrene resin of zinc phosphite replaces the styrene resin (Xi'an Blue Deep Resin) containing an iminodiethylzinc group.
  • the zinc ion/chelating resin-lithium manganate battery is substantially the same as the zinc ion/chelating resin-lithium manganate battery of the first embodiment of the present invention, except that in the preparation of the battery negative electrode, the A polyvinyl chloride resin (Aladdin) of a zinc amide group replaces a styrene resin (Xi'an Blue Deep Resin) containing an iminodiethylzinc group.
  • the zinc ion/chelating resin-lithium manganate battery is substantially the same as the zinc ion/chelating resin-lithium manganate battery of the first embodiment of the present invention, except that in the preparation of the battery negative electrode, the A polyacrylic resin (Aladdin) of a zinc amide diacetate group replaces a styrene resin (Xi'an Blue Deep Resin) containing an iminodiethylzinc group.
  • the zinc ion/chelating resin-lithium manganate battery is substantially the same as the zinc ion/chelating resin-lithium manganate battery of the first embodiment of the present invention, except that the acetic acid is contained in the preparation of the battery negative electrode.
  • a zinc group-based polyacrylic resin (Aladdin) replaces a styrene resin (Xi'an Blue Deep Resin) containing an iminodiethylzinc group.
  • the lead ion/chelating resin-lithium manganate battery of the embodiment 9 of the present invention is basically the same as the zinc ion/chelating resin-lithium manganate battery of the first embodiment of the present invention, and the difference is that when the battery negative electrode is prepared, Aminodiethyl lead styrene resin (Xi'an blue deep resin) replaces styrene resin containing iminodiethylzinc group (Xi'an Blue Deep Resin), replacing the zinc foil with lead foil.
  • Aminodiethyl lead styrene resin Xi'an blue deep resin
  • styrene resin containing iminodiethylzinc group Xi'an Blue Deep Resin
  • the nickel ion/chelating resin-lithium manganate battery is substantially the same as the zinc ion/chelating resin-lithium manganate battery of the first embodiment of the present invention, except that in the preparation of the battery negative electrode, the The styrene resin (Xi'an Blue Deep Resin) of the amine diethyl acetonitrile was substituted for the styrene resin (Xi'an Blue Deep Resin) containing an iminodiethylzinc group, and the zinc foil was replaced with a nickel foil.
  • the styrene resin (Xi'an Blue Deep Resin) of the amine diethyl acetonitrile was substituted for the styrene resin (Xi'an Blue Deep Resin) containing an iminodiethylzinc group, and the zinc foil was replaced with a nickel foil.
  • the zinc ion/chelating resin-lithium manganate battery is substantially the same as the zinc ion/chelating resin-lithium manganate battery of the fourth embodiment of the present invention, except that in the preparation of the battery negative electrode, the negative electrode film A layer of zinc foil was placed between the sheet and the anode current collector, and the specifications of the zinc foil were the same as those of the zinc foil used in the preparation of the anode in Example 1 of the present invention.
  • the zinc ion/chelating resin-lithium manganate battery of the embodiment 12 of the present invention is basically the same as the zinc ion/chelating resin-lithium manganate battery of the first embodiment of the present invention, except that when the battery negative electrode is prepared, the same is used.
  • Poly(vinyl chloride) resin of zinc iminodiacetic acid (Xi'an blue deep resin) and polystyrene resin containing zinc phosphate (Xi'an blue deep resin) the weight ratio of the two is 1:1, and the total resin content in the negative electrode is maintained. The same as the total content in Example 1, it was 80% by weight.
  • the zinc ion/chelating resin-lithium iron phosphate battery of the embodiment 13 of the present invention is basically the same as the zinc ion/chelating resin-lithium manganate battery of the first embodiment of the present invention, except that the positive electrode material is replaced by lithium iron phosphate. Lithium manganate in 1.
  • the zinc ion/chelating resin-lithium manganate battery of the embodiment 14 of the present invention is basically the same as the zinc ion/chelating resin-lithium manganate battery of the first embodiment of the present invention, except that the lithium cobalt oxide is used instead of the positive electrode material. Lithium manganate in Example 1.
  • Zinc ion/chelating resin-lithium manganate battery is basically the same as the zinc ion/chelating resin-lithium manganate battery of the first embodiment of the present invention, except that the negative electrode film and the negative electrode are prepared in the preparation of the battery negative electrode. No zinc foil is provided between the micron thick anode current collector stainless steel foil.
  • Zinc ion/chelating resin-lithium manganate battery was basically the same as the zinc ion/chelating resin-lithium manganate battery of Example 1 of the present invention, except that zinc foil was placed in the preparation of the battery negative electrode.
  • the surface of the 20 micrometer thick negative electrode current collector stainless steel foil facing away from the negative electrode membrane forms a battery negative electrode, and the positions of the negative electrode current collector and the zinc foil in Fig. 1(A) are interchanged.
  • Example 1 From the comparison of Example 1 and Comparative Example 2, it is known that the position where the zinc foil is placed has a great influence on the cycle performance and capacity of the battery. This is because if the anode membrane and the zinc foil are separated by the anode current collector, the loss of zinc ions in the anode membrane cannot be timely replenished by the zinc element, and the newly formed zinc ions also need to cross the anode current collector to reach the anode membrane. In the film, the efficiency is low.
  • Example 2 From the comparison of Example 1 with Example 2, it is known that the amino phosphate-containing resin has a better specific capacity and better cycle performance. This is because, compared to iminodiacetate, the amine phosphate has a stronger chelating ability for zinc ions, resulting in less zinc ion content in the electrolyte and improved cycleability. The same amount of phosphate is able to sequester more zinc ions, resulting in an increase in the specific capacity of the negative electrode.
  • Example 1 and Example 4 zinc powder as a supplement source of zinc ions can significantly increase the negative electrode compared with zinc foil. Specific capacity and cycle life. This is because the zinc foil can only replenish zinc ions to a part of the negative electrode active material that is in contact with it, and the zinc powder can be uniformly dispersed in the negative electrode, and the zinc ions are uniformly added to almost the entire negative electrode, so that the zinc powder has a better effect.
  • Example 6 From the comparison between Example 1 and Example 6, it is understood that the skeleton polymer is changed from styrene to vinyl chloride, and the capacity of the battery is drastically lowered. This is because the chelating group is more difficult to react with chlorine in vinyl chloride than the chloromethyl-styrene polymer backbone, so the density of the chelating group in the vinyl chloride resin is higher than that in the styrene resin. The density is much lower, resulting in lower capacity.
  • Example 7 From the comparison between Example 1 and Example 7, it is known that the skeleton polymer has styrene replaced by polyacrylic acid, the battery capacity is remarkably lowered, and the cycle life is also significantly lowered. This is because the amide group formed between the imine group and the carboxyl group is unstable, so that the density of the chelating group on the polyacrylic resin is low, and the zinc ion in the electrolytic solution cannot be effectively sequestered. In the cycle, the amide bond is easily hydrolyzed, resulting in deterioration of cycle performance.
  • Example 3 From the comparison between Example 3 and Example 8, it is understood that the skeleton polymer does not greatly affect the capacity and cycle performance of the negative electrode for the carboxyl group. This is because the carboxyl group has a higher density on two different polymer backbones, and the linked bonds are all stable covalent bonds, so the performance is close.
  • Example 9 It can be known from the results of Example 9 and Example 10 that the method for replenishing active metal ions with a simple element of the present invention is not only applicable to a battery of zinc ion/chelating resin, but also to many divalent metal ions/chelating resins.
  • the battery of the negative electrode As the battery of the negative electrode, the cycle life of the battery and the specific capacity of the negative electrode can be remarkably improved.
  • Example 11 From the results of Example 11, it is known that when zinc foil and zinc powder are simultaneously used as a supplementary source of zinc ions, the performance of the battery, including specific capacity and cycle performance, is substantially the same as that of the battery of Example 4, compared to the examples. Only zinc foil is used as a supplement source for zinc ions in 1 performance. It is indicated that in actual use, when zinc foil or zinc powder is used as a supplementary source of zinc ions, only one of them needs to be selected.
  • Example 12 From the results of Example 12, it can be known that when a polyvinyl chloride resin containing zinc iminodiacetic acid and a polystyrene resin containing zinc azinc phosphate are used as a complexing resin of zinc ions, the overall performance of the battery is between The battery of Example 6 containing the zinc iminodiacetic acid alone was used in combination with the battery of Example 2 in which the aminophosphonate-containing polystyrene resin was used alone. It is indicated that among the available chelating resins, the chelating resin with a large number of chelating groups per unit length of the backbone polymer and a strong chemical bond between the chelating group and the backbone polymer should be selected as much as possible in order to enhance the negative electrode. Specific capacity and cycle performance.
  • Table 2 shows the influence of the positive electrode material on the performance of the metal ion/chelating resin-lithium metal composite oxide battery. From the test results of Examples 1, 13, and 14 in Table 2, the metal ion/chelating resin of the present invention is known.
  • the positive electrode material in the lithium metal composite oxide battery is not limited to lithium manganate, and other lithium metal composite oxides such as lithium iron phosphate and lithium cobalt oxide can also be used as a positive electrode material in the battery system of the present invention and can be maintained. The battery system works properly.
  • the present invention has the following advantages over the prior art:
  • the metal element will slowly transform into active metal ions, supplementing the continuously lost active metal ions, thereby significantly increasing the metal ions/chelates.
  • the cycle life of the resin-lithium metal composite oxide battery keeps the capacity of the battery from decreasing as the cycle progresses.

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Abstract

本发明公开了一种金属离子/螯合树脂电池负极，其包括负极集流体和分布在负极集流体上的负极材料层，负极材料层包括骨架、固定在骨架上的螯合/吸附基团以及通过离子键或配位键形成于螯合/吸附基团上的金属离子，其中，负极集流体与负极材料层之间、负极材料层中、负极材料层远离负极集流体一侧中的至少一处设有可补充活性金属离子的对应的金属单质。此外，本发明还公开了一种金属离子/螯合树脂电池负极的制备方法和一种金属离子/螯合树脂-锂金属复合氧化物电池。

Description

金属离子/螯合树脂-锂金属复合氧化物电池及其负极 技术领域
本发明属于电池领域，更具体的说，本发明涉及一种具有理想循环性能的金属离子/螯合树脂-锂金属复合氧化物电池及其负极。
背景技术
金属离子/螯合树脂电池具有环保、低成本和安全等优点，因此近来获得了广泛的应用。
金属离子/螯合树脂负极含有大量的螯合树脂颗粒，螯合树脂颗粒会吸附电解液中的金属离子，使金属离子的浓度降低。此外，金属离子在循环过程中会转化为非活性的化合物，包括氧化物、氢氧化物等。随着金属离子的损失，电池的容量会随着循环的进行不断降低，导致电池的循环性能变差。
有鉴于此，确有必要提供一种具有理想循环性能的金属离子/螯合树脂-锂金属复合氧化物电池及其负极。
发明内容
本发明的目的在于：提供一种具有理想循环性能的金属离子/螯合树脂-锂金属复合氧化物电池及其负极。
为了实现上述发明目的，本发明提供了一种金属离子/螯合树脂电池负极，其包含负极集流体和分布在负极集流体上的负极材料层，负极材料层包括骨架、固定在骨架上的螯合/吸附基团以及通过离子键或配位键形成于螯合/吸附基团上的金属离子，其中，所述负极集流体与负极材料层之间、负极材料层中、负极材料层远离负极集流体一侧中的至少一处设有可补充活性金属离子的对应的金属单质。
作为本发明金属离子/螯合树脂电池负极的一种改进，所述金属单质选自锌、镁、铅、铬、锡、镉、铁、铜、钒或镍。
作为本发明金属离子/螯合树脂电池负极的一种改进，所述金属单质选自金属箔、金属粉、泡沫金属或金属网中的至少一种。
作为本发明金属离子/螯合树脂电池负极的一种改进，所述骨架选自聚苯乙烯树脂、聚氯乙烯树脂、聚甲基丙烯酸树脂、聚丙烯酸树脂、聚乙烯树脂或聚丙烯树脂中的至少一种。
作为本发明金属离子/螯合树脂电池负极的一种改进，所述螯合/吸附基团含有磷酸基团、亚胺基二乙酸基团或羧酸基团。
为了实现上述发明目的，本发明还提供了一种金属离子/螯合树脂-锂金属复合氧化物电池，其包括含有锂金属复合氧化物的正极、含有金属离子的负极、位于正极和负极间的隔离膜和电解液，其中，所述含有金属离子的负极为前述金属离子/螯合树脂电池负极。
作为本发明金属离子/螯合树脂-锂金属复合氧化物电池的一种改进，所述含锂金属复合氧化物选自锰酸锂、磷酸铁锂、钴酸锂、镍酸锂、镍钴锰酸锂中的至少一种。
此外，本发明还提供了一种金属离子/螯合树脂电池负极的制备方法，其包括以下步骤：
提供负极集流体；
制备含有骨架、固定在骨架上的螯合/吸附基团以及通过离子键或配位键形成于螯合/吸附基团上的活性金属离子的负极浆料；
将负极浆料压制、剪裁成含有负极材料层的负极膜片并烘干；以及
将负极膜片设置于负极集流体上制成金属离子/螯合树脂电池负极，其中，负极集流体与负极材料层之间、负极材料层中、负极材料层远离负极集流体一侧中的至少一处设有可补充活性金属离子的金属单质。
作为本发明金属离子/螯合树脂电池负极的制备方法的一种改进，所述金属单质选自锌、镁、铅、铬、锡、镉、铁、铜、钒或镍。
作为本发明金属离子/螯合树脂电池负极的制备方法的一种改进，所述金属单质选自金属箔、金属粉、泡沫金属或金属网中的至少一种。
作为本发明金属离子/螯合树脂电池负极的制备方法的一种改进，所述骨架选自聚苯乙烯树脂、聚氯乙烯树脂、聚甲基丙烯酸树脂、聚丙烯酸树脂、聚乙烯树脂或聚丙烯树脂中的至少一种。
作为本发明金属离子/螯合树脂电池负极的制备方法的一种改进，所述螯合/吸附基团含有磷酸基团、亚胺基二乙酸基团或羧酸基团中的至少一种。
相对于现有技术，本发明金属离子/螯合树脂-锂金属复合氧化物电池及其负极具有以下优点：在活性金属离子转变为非活性的金属化合物以后，金属单质会慢慢转变为活性金属离子，补充不断损失的活性金属离子，因此可显著提升金属离子/螯合树脂-锂金属复合氧化物电池的循环寿命，保持电池的容量不随循环的进行而降低。
附图说明
下面结合附图和实施例，对本发明金属离子/螯合树脂-锂金属复合氧化物电池及其负极进行详细说明，其中：
图1A和图1B分别为本发明实施例1金属离子/螯合树脂-锰酸锂电池的电池结构示意图和本发明实施例4金属离子/螯合树脂-锰酸锂电池的电池结构示意图。
图2为本发明实施例1和实施例4锌离子/螯合树脂-锰酸锂电池的充放电性能，其中，电压区间为1.5-2.3V。
实施例
为了使本发明的发明目的、技术方案和技术效果更加清晰，以下结合附图 和实施例，对本发明进一步详细说明。应当理解的是，本说明书中给出的实施例只是为了解释本发明，并不是为了限定本发明。
实施例1
正极的制备：将70wt％的正极材料锰酸锂粉末(300目)、20wt％的导电剂导电碳SP001和10wt％的粘结剂PTFE在去离子水中混合均匀，制成正极浆料；将正极浆料压制成膜片，膜片厚度为0.6mm，面积重量为500g/m2；将膜片裁剪成3×5cm2的正极膜片；在110-130℃的烘箱中去除正极膜片中的溶剂；将正极膜片与50微米厚的正极集流体不锈钢箔形成电池正极。
负极的制备：将含有亚胺基二乙锌基团的苯乙烯树脂(西安蓝深树脂)分散于无水乙醇中并置于球磨机中球磨4小时，球磨机转速为550rmp；将球磨后的树脂置于80℃烘箱中烘干，用筛网分离出200目以下的树脂粉末；将80wt％已过筛的负极材料树脂粉末、10wt％的导电剂导电碳SP001、7wt％的粘结剂PTFE、3wt％的增稠剂CMC在乙醇中混合均匀，制成负极浆料；将负极浆料压制成膜片，膜片厚度为1mm，面积重量为300g/m2；将膜片裁剪成3.1×5.1cm2的负极膜片；在70-120℃的烘箱中除去负极膜片中剩余的溶剂；将锌箔置于负极膜片与20微米厚的负极集流体不锈钢箔之间形成电池负极；压实电池负极，使集流体、锌箔、负极材料接触紧密，减小残存空气对电池的影响，增加负极材料与负极集流体之间的接触，减少负极的电阻，电池负极的结构如图1(A)所示。
电池的制备：将电池正极、电池负极、隔离膜组装成电池，注入1ml的电解液，在真空环境下密封，制成锌离子/螯合树脂-锰酸锂电池。
电池测试条件：将所组装的电池在1.5V-2.3V电压范围内以1C速率进行恒电流充放电，并计算其容量、比容量、库伦效率以及循环次数。
实施例2
本发明实施例2锌离子/螯合树脂-锰酸锂电池与本发明实施例1锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：在制备电池负极时，用含有胺基磷 酸锌的苯乙烯树脂(西安蓝深树脂)取代含有亚胺基二乙锌基团的苯乙烯树脂(西安蓝深树脂)。
实施例3
本发明实施例3锌离子/螯合树脂-锰酸锂电池与本发明实施例1锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：在制备电池负极时，用含有乙酸锌的苯乙烯树脂(西安蓝深树脂)取代含有亚胺基二乙锌基团的苯乙烯树脂(西安蓝深树脂)。
实施例4
正极的制备：将70wt％的正极材料锰酸锂粉末(300目)、20wt％的导电剂导电碳SP001和10wt％的粘结剂PTFE在去离子水中混合均匀，制成正极浆料；将正极浆料压制成膜片，膜片厚度为0.6mm，面积重量为500g/m2；将膜片裁剪成3×5cm2的正极膜片；在110-130℃的烘箱中去除正极膜片中的溶剂；将正极膜片与50微米厚的正极集流体不锈钢箔形成电池正极。
负极的制备：将含有亚胺基二乙锌基团的苯乙烯树脂(西安蓝深树脂)分散于无水乙醇中并置于球磨机中球磨4小时，球磨机转速为550rmp；将球磨后的树脂置于80℃烘箱中烘干，用筛网分离出200目以下的颗粒；将70wt％已过筛的负极材料树脂粉末、10wt％的导电剂导电碳SP001、10wt％的200目锌粉、7wt％的粘结剂PVDF、3wt％的增稠剂CMC在乙醇中混合均匀，制成负极浆料；将负极浆料压制成膜片，膜片厚度为0.6mm，面积重量为400g/m2；将膜片裁剪成3.1×5.1cm2的负极膜片；在70-120℃的烘箱中去除负极膜片中剩余的溶剂；将负极膜片与20微米厚的集流体不锈钢箔形成电池负极；压实电池负极，使负极集流体、锌粉与负极材料的复合层接触紧密，减小残存空气对电池的影响，增加负极材料与负极集流体之间的接触，减少负极的电阻，电池负极的结构如图1(B)所示。
电池的制备：将电池正极、电池负极、隔离膜组装成电池，注入1ml的电 解液，在真空环境下密封，制备成锌离子/螯合树脂-锰酸锂电池。
实施例5
本发明实施例5锌离子/螯合树脂-锰酸锂电池与本发明实施例4锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：在制备电池负极时，用含有胺基磷酸锌的苯乙烯树脂(西安蓝深树脂)取代含有亚胺基二乙锌基团的苯乙烯树脂(西安蓝深树脂)。
实施例6
本发明实施例6锌离子/螯合树脂-锰酸锂电池与本发明实施例1锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：在制备电池负极时，用含有亚胺基二乙酸锌基团的聚氯乙烯树脂(阿拉丁)取代含有亚胺基二乙锌基团的苯乙烯树脂(西安蓝深树脂)。
实施例7
本发明实施例7锌离子/螯合树脂-锰酸锂电池与本发明实施例1锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：在制备电池负极时，用含有亚胺基二乙酸锌基团的聚丙烯酸树脂(阿拉丁)取代含有亚胺基二乙锌基团的苯乙烯树脂(西安蓝深树脂)。
实施例8
本发明实施例8锌离子/螯合树脂-锰酸锂电池与本发明实施例1锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：在制备电池负极时，用含有乙酸锌基团的聚丙烯酸树脂(阿拉丁)取代含有亚胺基二乙锌基团的苯乙烯树脂(西安蓝深树脂)。
实施例9
本发明实施例9铅离子/螯合树脂-锰酸锂电池与本发明实施例1锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：在制备电池负极时，用含有亚胺基二乙铅的苯乙烯树脂(西安蓝深树脂)取代含有亚胺基二乙锌基团的苯乙烯树脂 (西安蓝深树脂)，用铅箔取代锌箔。
实施例10
本发明实施例10镍离子/螯合树脂-锰酸锂电池与本发明实施例1锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：在制备电池负极时，用含有亚胺基二乙镍的苯乙烯树脂(西安蓝深树脂)取代含有亚胺基二乙锌基团的苯乙烯树脂(西安蓝深树脂)，用镍箔取代锌箔。
实施例11
本发明实施例11锌离子/螯合树脂-锰酸锂电池与本发明实施例4锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：在制备电池负极时，在负极膜片和负极集流体之间还放入一层锌箔，锌箔规格与本发明实施例1中制备负极时使用的锌箔规格相同。
实施例12
本发明实施例12锌离子/螯合树脂-锰酸锂电池与本发明实施例1锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：在制备电池负极时，同时使用含有亚胺基二乙酸锌的聚氯乙烯树脂(西安蓝深树脂)和含有磷酸锌的聚苯乙烯树脂(西安蓝深树脂)，二者的重量比为1：1，负极中的树脂总含量保持与实施例1中的总含量相同，为80wt％。
实施例13
本发明实施例13锌离子/螯合树脂-磷酸铁锂电池与本发明实施例1锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：正极材料采用磷酸铁锂替代实施例1中的锰酸锂。
实施例14
本发明实施例14锌离子/螯合树脂-锰酸锂电池与本发明实施例1锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：正极材料中采用钴酸锂替代实施例1中的锰酸锂。
对比例1
对比例1锌离子/螯合树脂-锰酸锂电池与本发明实施例1锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：在制备电池负极时，负极膜片与20微米厚的负极集流体不锈钢箔之间未设置锌箔。
对比例2
对比例2锌离子/螯合树脂-锰酸锂电池与本发明实施例1锌离子/螯合树脂-锰酸锂电池基本相同，不同之处在于：在制备电池负极时，将锌箔置于背离负极膜片的20微米厚的负极集流体不锈钢箔表面形成电池负极，既图1(A)中负极集流体与锌箔的位置互换。
结果分析
表1实施例和对比例金属离子/螯合树脂-锂金属复合氧化物电池的测试结果
Figure PCTCN2016083758-appb-000001
请参阅表1所示测试结果，从实施例1、4与对比例1的对比可知，加入锌单质做为锌离子的补充源，电池的循环性能得到显著改善。这是因为，在对比例1中，活性锌离子会逐渐转化为非活性的锌化合物，使得电池容量发生不可逆转的降低，导致没有锌单质的电池循环性能特别差。由于锌单质也部分的是 电池中的活性物质，电池的容量也会得到一定的提升。
从实施例1与对比例2的对比可知，锌箔放置的位置对电池的循环性能和容量有很大影响。这是因为，如果负极膜片与锌箔被负极集流体隔开，负极膜片里面的锌离子的损失不能得到锌单质的及时补充，新生成的锌离子也需要跨越负极集流体才能到达负极膜片中，效率低下。
从实施例1与实施例2的对比可知，含有胺基磷酸根的树脂有更好的比容量和更好的循环性能。这是由于，相比于亚胺基二乙酸根，胺基磷酸根对锌离子有更强的螯合能力，导致电解液中的锌离子含量更少，循环能力得到提升。同样数量的磷酸根能够螯合住更多的锌离子，使得负极的比容量得到提升。
请结合参照图2所示，从实施例1与实施例4，以及实施例2与实施例5的对比中可知，相较于锌箔，锌粉做为锌离子的补充源能够显著增加负极的比容量和循环寿命。这是由于锌箔只能对与其接触的一部分负极活性物质补充锌离子，而锌粉能够在负极中均匀分散开，为几乎整个负极均匀补充锌离子，因此具有更好的效果。
从实施例1与实施例6的对比可知，骨架高分子由苯乙烯换成氯乙烯，电池的容量急剧下降。这是因为，相较于氯代甲基对苯乙烯高分子骨架，螯合基团更难与氯乙烯中的氯发生反应，因此螯合基团在氯乙烯树脂中的密度比在苯乙烯树脂中的密度要低很多，导致容量较低。
从实施例1与实施例7的对比可知，骨架高分子有苯乙烯换成聚丙烯酸，电池容量有显著下降，循环寿命也有明显下降。这是因为，亚胺基与羧基之间形成的酰胺基团不稳定，使得聚丙烯酸树脂上的螯合基团密度较低，不能有效螯合电解液中的锌离子。在循环中，酰胺键容易水解，导致循环性能变差。
从实施例3与实施例8的对比可知，对于羧基基团，骨架高分子对负极的容量和循环性能没有很大的影响。这是因为，羧基基团在两个不同高分子骨架上面都有较高的密度，且连接的键均为稳定的共价键，所以性能接近。
从实施例9与实施例10的结果可以知道，本发明用金属单质补充活性金属离子的方法不仅仅适用于锌离子/螯合树脂的电池，也适用于很多二价的金属离子/螯合树脂作为负极的电池，且可以显著提升电池的循环寿命和负极的比容量。
从实施例11的结果可以知道，在同时使用锌箔和锌粉做为锌离子的补充源时，电池的性能，包括比容量和循环性能，与实施例4的电池性能基本相同，比实施例1中只使用锌箔做为锌离子的补充源性能要好。表明在实际使用中，在使用锌箔或者锌粉做为锌离子的补充源时，只需要选择其中的一种即可。
从实施例12的结果可以知道，同时使用含有亚胺基二乙酸锌的聚氯乙烯树脂和含有胺基磷酸锌的聚苯乙烯树脂做为锌离子的络合树脂时，电池的综合性能介于单独使用含有亚胺基二乙酸锌的聚氯乙烯树脂的实施例6的电池综合性能和单独使用含有胺基磷酸锌的聚苯乙烯树脂的实施例2的电池综合性能之间。表明在可供选择的螯合树脂中，应尽可能的选择单位长度骨架高分子上螯合基团数量多、螯合基团与骨架高分子间连接化学键强的螯合树脂，以期提升负极的比容量和循环性能。
表2正极材料对金属离子/螯合树脂-锂金属复合氧化物电池性能的影响
Figure PCTCN2016083758-appb-000002
表2所示为正极材料对金属离子/螯合树脂-锂金属复合氧化物电池性能的影响，从表2中的实施例1、13、14的测试结果可知，本发明金属离子/螯合树脂-锂金属复合氧化物电池中的正极材料不限于锰酸锂，其他的锂金属复合氧化物，如磷酸铁锂和钴酸锂，也可以用作本发明电池体系的中的正极材料且能保持电池体系的正常工作。
结合以上对本发明实施例的详细描述可以看出，相对于现有技术，本发明具有以下优点：
用螯合树脂类的金属离子负极组装成的电池，随着循环的进行，负极中的金属会慢慢转化成非活性的金属化合物，从而导致电池容量随着循环的进行而不断降低。采用本发明的方法补充活性金属离子，在活性金属离子转变为非活性的金属化合物以后，金属单质会慢慢转变为活性金属离子，补充不断损失的活性金属离子，因此可显著提升金属离子/螯合树脂--锂金属复合氧化物电池的循环寿命，保持电池的容量不随循环的进行而降低。
根据上述原理，本发明还可以对上述实施方式进行适当的变更和修改。因此，本发明并不局限于上面揭示和描述的具体实施方式，对本发明的一些修改和变更也应当落入本发明的权利要求的保护范围内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本发明构成任何限制。

Claims (12)

  1. 一种金属离子/螯合树脂电池负极，包含负极集流体和分布在负极集流体上的负极材料层，负极材料层包括骨架、固定在骨架上的螯合/吸附基团以及通过离子键或配位键形成于螯合/吸附基团上的金属离子，其特征在于：所述负极集流体与负极材料层之间、负极材料层中、负极材料层远离负极集流体一侧中的至少一处设有可补充活性金属离子的对应的金属单质。
  2. 根据权利要求1所述的金属离子/螯合树脂电池负极，其特征在于：所述金属单质选自锌、镁、铅、铬、锡、镉、铁、铜、钒或镍。
  3. 根据权利要求1所述的金属离子/螯合树脂电池负极，其特征在于：所述金属单质选自金属箔、金属粉、泡沫金属或金属网中的至少一种。
  4. 根据权利要求1所述的金属离子/螯合树脂电池负极，其特征在于：所述骨架选自聚苯乙烯树脂、聚氯乙烯树脂、聚甲基丙烯酸树脂、聚丙烯酸树脂、聚乙烯树脂或聚丙烯树脂中的至少一种。
  5. 根据权利要求1所述的金属离子/螯合树脂电池负极，其特征在于：所述螯合/吸附基团含有磷酸基团、亚胺基二乙酸基团或羧酸基团中的至少一种。
  6. 一种金属离子/螯合树脂-锂金属复合氧化物电池，其包括含有锂金属复合氧化物的正极、含有金属离子的负极、位于正极和负极之间的隔离膜和电解液，其特征在于：所述含有金属离子的负极为权利要求1至5中任一项所述的金属离子/螯合树脂电池负极。
  7. 根据权利要求6所述的金属离子/螯合树脂-锂金属复合氧化物电池，其特征在于：所述锂金属复合氧化物选自锰酸锂、磷酸铁锂、钴酸锂、镍酸锂、镍钴锰酸锂中的至少一种。
  8. 一种金属离子/螯合树脂电池负极的制备方法，其包括以下步骤：
    提供负极集流体；
    制备含有骨架、固定在骨架上的螯合/吸附基团以及通过离子键或配位键形成于螯合/吸附基团上的活性金属离子的负极浆料；
    将负极浆料压制、剪裁成含有负极材料层的负极膜片并烘干；以及
    将负极膜片设置于负极集流体上制成金属离子/螯合树脂电池负极，其中，负极集流体与负极材料层之间、负极材料层中、负极材料层远离负极集流体一侧中的至少一处设有可补充活性金属离子的对应的金属单质。
  9. 根据权利要求8所述的金属离子/螯合树脂电池负极的制备方法，其特征在于：所述金属单质选自锌、镁、铅、铬、锡、镉、铁、铜、钒或镍。
  10. 根据权利要求8所述的金属离子/螯合树脂电池负极的制备方法，其特征在于：所述金属单质选自金属箔、金属粉、泡沫金属或金属网中的至少一种。
  11. 根据权利要求8所述的金属离子/螯合树脂电池负极的制备方法，其特征在于：所述骨架选自聚苯乙烯树脂、聚氯乙烯树脂、聚甲基丙烯酸树脂、聚丙烯酸树脂、聚乙烯树脂或聚丙烯树脂中的至少一种。
  12. 根据权利要求8所述的金属离子/螯合树脂电池负极的制备方法，其特征在于：所述螯合/吸附基团含有磷酸基团、亚胺基二乙酸基团或羧酸基团中的至少一种。
PCT/CN2016/083758 2016-05-27 2016-05-27 金属离子/螯合树脂-锂金属复合氧化物电池及其负极 Ceased WO2017201758A1 (zh)

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CN112813270A (zh) * 2020-12-30 2021-05-18 江苏海普功能材料有限公司 废旧镍钴锰三元锂电池正极材料回收方法

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CN104659342A (zh) * 2013-11-21 2015-05-27 南京精研新能源科技有限公司 一种二次电池负极材料

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CN104659342A (zh) * 2013-11-21 2015-05-27 南京精研新能源科技有限公司 一种二次电池负极材料

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112813270A (zh) * 2020-12-30 2021-05-18 江苏海普功能材料有限公司 废旧镍钴锰三元锂电池正极材料回收方法

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