WO2020233264A1 - 一种气体吸附剂、二次电池及装置 - Google Patents

一种气体吸附剂、二次电池及装置 Download PDF

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WO2020233264A1
WO2020233264A1 PCT/CN2020/083633 CN2020083633W WO2020233264A1 WO 2020233264 A1 WO2020233264 A1 WO 2020233264A1 CN 2020083633 W CN2020083633 W CN 2020083633W WO 2020233264 A1 WO2020233264 A1 WO 2020233264A1
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gas adsorbent
gas
secondary battery
cuprous
porous material
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French (fr)
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姜玲燕
葛销明
林冬燕
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Contemporary Amperex Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B01J20/0237—Compounds of Cu
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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

  • This application belongs to the field of battery technology, and more specifically relates to a gas adsorbent, a secondary battery and a device.
  • New energy vehicles have developed vigorously due to their energy-saving and environmentally friendly features.
  • its large-scale industrialization faces several major problems, including high costs, mileage anxiety and low energy density.
  • New energy vehicles are mainly composed of battery drive system, motor system, electronic control system and assembly.
  • the motor, electronic control and assembly are basically the same as those of traditional fuel vehicles, and the reason for the price difference lies in the battery drive system.
  • Battery drive systems account for 30-45% of the cost of new energy vehicles, and power secondary batteries account for about 75-85% of the cost of battery drive systems.
  • the power secondary battery is composed of a positive electrode, a negative electrode, a non-aqueous electrolyte and a separator.
  • ternary nickel-cobalt-manganese materials NCM
  • LFP lithium iron phosphate
  • gas production in NCM system secondary batteries has always been a serious problem.
  • the gas production mechanism is very complicated, which comes from many reasons, and is related to the positive electrode, the negative electrode, and the electrolyte.
  • the positive electrode potential of NCM as a positive electrode material is relatively high, and the non-aqueous solvent in the electrolyte is easy to decompose under the working environment.
  • the gas generated inside the battery contains CO 2 , CO, CH 4 , C 2 H 4 , C 2 H 6 , H 2 and other components.
  • CO 2 and CO account for the largest proportion.
  • the electrolyte formula can be improved to form an inorganic salt protective film on the surface of the positive and negative electrodes to reduce side reactions of the positive and negative electrodes at high temperatures, thereby reducing gas production, but the formed inorganic salt protective film has higher impedance and poor wettability. It is also necessary to add additional additives to improve impedance and wettability for synergistic effect, which greatly increases the complexity and cost of the components in the electrolyte. Since the decomposition of non-aqueous solvents is unavoidable from a thermodynamic point of view, some solution mechanism needs to be found at the cell level to absorb the gas generated in the cell to reduce the internal pressure of the cell.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2008-146963 discloses a secondary battery in which a gas adsorbent is added to a separator substrate.
  • Patent Document 2 (PCT WO2011/135818JA2011.11.03) discloses a gas adsorption layer in which a structural material containing an inorganic substance and a binder are added to a positive electrode or a negative electrode.
  • the methods of Patent Documents 1 and 2 are to mix a gas adsorbent into the separator substrate or pole pieces, but these two methods may damage the porosity of the separator, reduce thermal stability, and reduce the internal resistance and reaction activity of the positive electrode/negative electrode.
  • Patent Document 3 (Chinese Patent Application CN106159122A) discloses a battery shell structure, including a gas adsorption layer, a first adhesive layer, a gas barrier layer, a second adhesive layer and an outer protective layer. But this kind of battery shell structure is very complicated, mass production manufacturability is very poor, and the cost is high.
  • the gas adsorbent needs to be able to quickly react with CO in the gas generated inside the battery to reduce the pressure in the battery, and
  • the use of the gas adsorbent in a secondary battery requires a simple structure, so that the secondary battery has both thermal stability, good separator porosity, and positive/negative internal resistance and reaction activity.
  • a gas adsorbent which includes a cuprous ion compound and a porous material.
  • a method for preparing a gas adsorbent which can quickly and efficiently prepare the gas adsorbent of the first aspect of the present application.
  • a secondary battery which includes the gas adsorbent of the first aspect of the present application.
  • a method for preparing a secondary battery is provided, which can quickly and efficiently manufacture the secondary battery of the third aspect of the present application.
  • a device which includes the secondary battery of the third aspect of the present application.
  • the gas adsorbent has both high specific surface area and chemical properties of complex reaction with CO, and can
  • the device of the present application includes the secondary battery provided by the present application, and thus has at least the same advantages as the secondary battery.
  • Fig. 1 is a schematic diagram of an embodiment of a secondary battery.
  • Figure 2 is an exploded view of Figure 1.
  • Fig. 3 is a schematic diagram of an embodiment of a battery module.
  • Fig. 4 is a schematic diagram of an embodiment of a battery pack.
  • Fig. 5 is an exploded view of Fig. 4.
  • Fig. 6 is a schematic diagram of an embodiment of a device in which a secondary battery is used as a power source.
  • the first aspect of the present application provides a gas adsorbent, which includes a cuprous ion compound and a porous material.
  • the gas adsorption rate of the gas adsorbent is 0.4-1 mmol/h, preferably 0.7-1 mmol/h.
  • cuprous ion compound in the gas adsorbent is to provide cuprous ions.
  • the cuprous ions can undergo a complex reaction with the main gas CO whose pressure inside the cell increases, and consume the main gas CO produced.
  • the function of the porous material The main purpose is to provide a microporous support matrix with appropriate pore size to achieve a high gas adsorbent specific surface area that meets the requirements, and capture and adsorb CO, CO 2 and other major gases.
  • the principle of the complex reaction between cuprous ions and CO is: there is a lone pair of electrons on the C of CO.
  • cuprous ion compounds and porous materials need to meet certain gas adsorption rate requirements, thereby reducing the air pressure generated inside the cell, so as to achieve the purpose of reducing cell swelling and interface impedance, and extending the service life of the cell.
  • the oxo acid salt or inorganic salt of the cuprous ion is used.
  • the cuprous ion compound is selected from one or more of cuprous oxide, cuprous sulfide, cuprous carboxylate, cuprous sulfate, cuprous carbonate and cuprous nitrate.
  • the porous material is selected from one or more of A-type, Y-type, X-type, ZSM-type molecular sieves and aluminum phosphate molecular sieves.
  • Molecular sieves are currently porous materials with large specific surface area and low cost.
  • the pore size of the porous material is Preferably This pore size range allows CO molecules to enter the porous material, and can minimize the electrolyte solvent molecules from entering the porous material.
  • the pore size of the porous material is improperly selected (over Outside the range), although the purpose of this application can be achieved to a certain extent, its performance is not outstanding enough. This is because the solvent molecules of the electrolyte will be continuously absorbed by the porous material and cause its saturation, thereby losing the CO and CO 2 Capture ability, so special attention needs to be paid to the selection of porous materials with high specific surface area or the selection of closed membranes.
  • the specific surface area of the porous material is 400-1000 m 2 /g, preferably 800-1000 m 2 /g.
  • the weight ratio of the cuprous ion compound to the porous material is 1:10-1:1, preferably 1:4-1:2.
  • the weight ratio of the cuprous ion compound and the porous material is very important for the effective realization of the purpose of this application. If the ratio of the two is not appropriate, although the purpose of this application can be achieved, it will have a certain influence on the gas absorption effect.
  • the total amount of the cuprous ion compound is 6 ⁇ 10 -6 -6 ⁇ 10 -5 mol, preferably 8 ⁇ 10 -6 -2 ⁇ 10 -5 mol.
  • the generation of gas in the battery is related to the capacity of the battery cell. Therefore, the total amount of the cuprous ion compound needs to be controlled within a certain range to achieve the dual performance of effective gas absorption and reasonable control of the battery weight.
  • the gas adsorbent of the present invention is prepared by a method including the following process: in an environment that is isolated from water and oxygen, the cuprous ion compound and the porous material are mixed and stirred, and then the cuprous ion The compound melts to obtain the gas adsorbent.
  • the second aspect of the application is to provide a method for preparing the above-mentioned gas adsorbent, which includes: mixing and stirring the cuprous ion compound with a porous material in an environment that is isolated from water and oxygen, and then melting the cuprous ion compound , To obtain the gas adsorbent.
  • a third aspect of the present application provides a secondary battery, which includes the gas adsorbent described in the first aspect of the present application.
  • the secondary battery in the present application refers to a battery that can be used repeatedly in charge and discharge cycles, including but not limited to lithium ion batteries, sodium ion batteries, and the like.
  • the gas adsorbent described in the first aspect of the present application is encapsulated in a porous gas-permeable film and placed in the battery cell of the secondary battery; more preferably, it is placed in the top seal space of the battery cell of the secondary battery.
  • the porous air-permeable film is one or more of microporous membranes, woven films, non-woven films, fiber paper, laminated films and composite films. These films have low cost, suitable thickness and pore size, strong manufacturability, and strength to meet the requirements.
  • the pore size of the porous breathable film is Preferably The pore size of the porous and gas-permeable membrane allows CO molecules to pass through the membrane, and can prevent electrolyte solvent molecules from passing through the membrane to the greatest extent.
  • the solvent molecules of the electrolyte will be continuously absorbed by the porous and gas-permeable film, resulting in saturation, thereby losing the ability to capture CO and CO 2. Therefore, special attention should be paid to the selection of a porous and gas-permeable film with a high specific surface area or the selection of a closed film.
  • the secondary battery of the present application also includes a positive pole piece, a negative pole piece, a separator and an electrolyte.
  • active ions are inserted and extracted back and forth between the positive pole piece and the negative pole piece.
  • the isolation film is arranged between the positive pole piece and the negative pole piece to play a role of isolation.
  • the electrolyte conducts ions between the positive pole piece and the negative pole piece.
  • the structure and manufacturing method of the secondary battery of the present application are known per se. The technical personnel of the present application can select suitable materials according to the application requirements to prepare the above-mentioned positive pole piece, negative pole piece, separator and electrolyte.
  • Fig. 1 shows a secondary battery 5 having a square structure as an example.
  • the secondary battery may include an outer package for packaging the positive pole piece, the negative pole piece, the separator and the electrolyte.
  • the outer packaging of the secondary battery may be a soft bag, such as a pouch type soft bag.
  • the material of the soft bag can be plastic, for example, it can include one or more of polypropylene PP, polybutylene terephthalate PBT, polybutylene succinate PBS, and the like.
  • the outer packaging of the secondary battery may also be a hard shell, such as a hard plastic shell, aluminum shell, steel shell, and the like.
  • the outer package may include a housing 51 and a cover 53.
  • the housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose a receiving cavity.
  • the housing 51 has an opening communicating with the containing cavity, and a cover plate 53 can cover the opening to close the containing cavity.
  • the positive pole piece, the negative pole piece, and the separator may be formed into the cell 52 through a winding process or a lamination process.
  • the battery core 52 is encapsulated in the containing cavity.
  • the electrolyte is infiltrated in the cell 52.
  • the number of battery cells 52 contained in the secondary battery 5 can be one or several, which can be adjusted according to requirements.
  • the secondary battery can be assembled into a battery module, and the number of secondary batteries contained in the battery module can be multiple, and the specific number can be adjusted according to the application and capacity of the battery module.
  • FIG. 3 is a battery module 4 as an example.
  • a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4. Of course, it can also be arranged in any other manner. Furthermore, the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having an accommodation space, and a plurality of secondary batteries 5 are accommodated in the accommodation space.
  • the above-mentioned battery modules can also be assembled into a battery pack, and the number of battery modules contained in the battery pack can be adjusted according to the application and capacity of the battery pack.
  • the battery pack 1 may include a battery box and a plurality of battery modules 4 provided in the battery box.
  • the battery box includes an upper box body 2 and a lower box body 3.
  • the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4.
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the fourth aspect of the present application provides a method for preparing a secondary battery, including the steps of encapsulating the gas adsorbent of the first aspect in a porous gas-permeable film and placing it in a battery cell of the secondary battery.
  • it includes the step of encapsulating the gas adsorbent of the first aspect into a porous gas-permeable film and placing it in the top seal space of the cell of the secondary battery.
  • a fifth aspect of the present application provides a device, which includes the secondary battery described in the third aspect of the present application.
  • the secondary battery can be used as a power source of the device, and can also be used as an energy storage unit of the device.
  • the device can be, but is not limited to, mobile devices (such as mobile phones, laptop computers, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf Vehicles, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc.
  • the device can select a secondary battery, battery module, or battery pack according to its usage requirements.
  • Figure 6 is a device as an example.
  • the device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle.
  • a battery pack or battery module can be used.
  • the device may be a mobile phone, a tablet computer, a notebook computer, etc.
  • the device is generally required to be thin and light, and a secondary battery can be used as a power source.
  • the batteries of Examples 1-14 and Comparative Examples 1-2 were prepared according to the following methods.
  • the positive electrode active material LiNi 1/3 Co 1/3 Mn 1/3 O 2 , the conductive agent Super-P, and the binder polyvinylidene fluoride (PVDF) are mixed in a mass ratio of 94:3:3, and the solvent N- Methylpyrrolidone (NMP), stir under the action of a vacuum mixer until the system is uniform to obtain the positive electrode slurry; evenly coat the positive electrode slurry on the two surfaces of the positive electrode current collector aluminum foil, dry at room temperature and transfer to the oven to continue After drying, cold pressing and slitting, a positive pole piece is obtained.
  • Ethylene carbonate (EC) and ethyl methyl carbonate (EMC) are mixed in a volume ratio of 3:7 to obtain an organic solvent, and then fully dried LiPF 6 is dissolved in the mixed organic solvent to prepare a concentration of 1 mol/L Of electrolyte.
  • cuprous ion compound shown in Table 1 with the porous material in an environment where there is no CO, CO 2 , O 2 , H 2 O and other oxidizing substances, and separate moisture and oxygen in a sealed container for stirring 1- 24h, get uniform mixed powder, heat for 1-24h at high temperature (80-750°C), cuprous ion compound powder melts at high temperature, and evenly penetrates into the inside and surface of porous material with high specific surface, that is The gas adsorbent.
  • the parameters shown in Table 1 are as follows ( 5)
  • the prepared gas adsorbent is packaged into the microporous membranes with different pore diameters as shown in Table 1, and placed in the inner top sealing space of the battery cell of the secondary battery, and the bare cell is placed in the outer packaging shell, after drying
  • the electrolyte is injected, and the secondary battery is obtained after vacuum packaging, standing, forming, and shaping.
  • the following describes the experimental measurement method of the internal gas pressure and the gas adsorption rate of the cell of the secondary battery containing the gas adsorbent.
  • Examples 1-5 show that the effect of prolonging the battery life of high-temperature storage and gas production is related to the weight ratio of cuprous ion compound to porous material, and the weight ratio of cuprous ion compound to porous material is 1:4 The best effect is in the range of -1:2. If the weight ratio of the cuprous ion compound to the porous material is too high, that is, if there is too much cuprous ion compound, the surplus part will not be distributed on the surface of the porous material.
  • This part will not be able to effectively absorb CO, such as the weight of the cuprous ion compound and the porous material If the ratio is too low, there are too many porous materials, and there will be no cuprous ion compound distributed on the surface of a part of the porous material, and this part of the porous material will not function effectively.
  • Examples 3 and 6 show that the effect of prolonging the life of the cell during high-temperature storage and gas production is related to the type of porous material, and type A is better than type X.
  • Examples 6 and 7 illustrate that the effect of prolonging the life of the battery during high-temperature storage and gas production is related to the types of cuprous ion compounds, and that cuprous sulfide has a better effect than cuprous chloride.
  • Examples 5, 8, and 9 illustrate that the effect of prolonging the life of the battery during high temperature storage and gas production is related to the pore size of the porous material.
  • the effect is best within the range.
  • the pore size can allow CO molecules to enter the porous material, and can avoid the electrolyte solvent molecules from entering the porous material to the greatest extent.
  • the solvent molecules of the electrolyte are too much absorbed by the porous material and cause its saturation, which will make it porous The material loses its ability to capture CO and CO 2 .
  • Examples 8, 10, and 11 illustrate that the effect of prolonging the life of the battery during high-temperature storage and gas production is related to the porous, breathable and thin pore size.
  • the pore size can allow CO molecules to pass through the membrane, and can avoid the electrolyte solvent molecules from penetrating the membrane to the greatest extent.
  • the electrolyte solvent molecules pass through the membrane too much and are absorbed by the porous and breathable membrane. Its saturation will cause the porous and breathable film to lose its ability to capture CO and CO 2 .
  • Examples 10, 12-14 illustrate that the effect of prolonging the life of the battery during high temperature storage and gas production is related to the ratio of the total amount of cuprous ion compounds to the cell capacity.
  • the ratio of the total amount of cuprous ion compounds to the cell capacity is 8 ⁇
  • the effect is best in the range of 10 -6 -2 ⁇ 10 -5 . If it is too small, the gas cannot be absorbed completely, and if it is too much, the adsorbent will have a surplus, which will reduce the energy density of the cell.
  • the adsorbent without cuprous ion compound or porous material has no effect of prolonging the life of the battery during high temperature storage and gas production.

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Abstract

本申请属于电池技术领域，更具体地涉及一种气体吸附剂、二次电池及装置，所述气体吸附剂包括亚铜离子化合物和多孔材料。所述气体吸附剂兼具高比表面积和与CO发生络合反应的化学性能，能够及时降低电芯的极片与电解液之间相互作用生成气体导致的内部气压，减少电芯鼓胀和界面阻抗，并延长电芯的使用寿命，用多孔的可透气薄膜将该气体吸附剂封装，置于电芯内部，该结构简单易于产业化生产制造。

Description

一种气体吸附剂、二次电池及装置
本申请要求于2019年5月23日提交中国专利局、申请号为201910432386.6、申请名称为“一种可延长锂离子电池寿命的气体吸附剂及其锂离子电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请属于电池技术领域，更具体地涉及一种气体吸附剂、二次电池及装置。
背景技术
近年来，新能源汽车因其节能和环保的特性得到蓬勃发展。但是其大规模产业化面临几大问题，包括居高不下的成本、里程焦虑和低能量密度。新能源汽车主要由电池驱动系统、电机系统和电控系统及组装等部分组成。其中电机、电控及组装和传统燃油车基本相同，差价的原因在于电池驱动系统。电池驱动系统占据了新能源汽车成本的30-45％，而动力二次电池又占据电池驱动系统约75-85％的成本。
动力二次电池由正极、负极、非水性电解液和隔离膜组成，在乘用车领域，三元镍钴锰材料(NCM)作为正极材料已经成为市场主流。这是由于NCM的能量密度高于磷酸铁锂(LFP)，可以在有限的空间内提供更多的能量，从而克服里程焦虑。然而，NCM体系二次电池中产气一直是一个严重的问题。其产气机理十分复杂，来源于多方面原因，与正极、负极、电解液均有一定关联，例如：NCM作为正极材料的正极电位较高，电解液中的非水溶剂在工作环境下容易分解，电池内部生成的气体中含有CO 2、CO、CH 4、C 2H 4、C 2H 6、H 2等成分。对于NCM体系电芯来说，CO 2和CO占比最大。
可以通过改善电解液配方，使正负极表面形成无机盐保护膜，以减少高温下正负极的副反应，从而降低产气，但形成的无机盐保护膜阻抗较高且浸润性较差，还需要额外加入改善阻抗与浸润性的添加剂进行协同作用，使得电解液中的成分复杂程度及成本都大大提高。由于非水溶剂的分解在热力学 角度来说是不可避免的，所以在电芯层级需要找到某些解决机制，以吸收电芯内产生的气体从而降低电芯的内部压力。
专利文献1(日本特开2008-146963号公报)公开了在隔膜基材中添加气体吸附剂的二次电池。专利文献2(PCT WO2011/135818JA2011.11.03)公开了一种在正极或负极极片中添加包含无机物的结构材料和粘结剂的气体吸附层。专利文献1和2的做法是在隔膜基材或极片中混入气体吸附剂，但这两种做法可能会损害隔膜的孔隙率，降低热稳定性，降低正极/负极的内阻和反应活性。
专利文献3(中国专利申请CN106159122A)公开了一种电池壳层结构，包括气体吸附层，第一接着层，阻气层，第二接着层及外保护层。但这种电池壳层结构非常复杂，量产可制造性很差，且成本高昂。
发明内容
鉴于背景技术存在的上述问题，需要提供一种气体吸附剂、二次电池及装置，所述气体吸附剂需能够快速与电池内部生成的气体中的CO发生反应，使电芯中气压下降，并且该气体吸附剂在二次电池中的使用必需结构简单，使二次电池兼具热稳定性、良好的隔膜孔隙率和正极/负极的内阻和反应活性。
为实现上述目的，在本申请的第一方面，提供一种气体吸附剂，包括亚铜离子化合物和多孔材料。
在本申请的第二个方面，提供一种气体吸附剂的制备方法，能够快速高效的制备本申请第一方面的气体吸附剂。
在本申请的第三方面，提供一种二次电池，其包括本申请第一方面的气体吸附剂。
在本申请的第四方面，提供一种二次电池的制备方法，能够快速高效的制备本申请第三方面的二次电池。
在本申请的第五方面，提供一种装置，其包括本申请第三方面的二次电池。
与现有技术相比，本申请的技术方案至少具有以下有益效果：
所述气体吸附剂兼具高比表面积和与CO发生络合反应的化学性能，能够
及时降低电芯的极片与电解液之间相互作用生成气体导致的内部气压， 减少电芯鼓胀和界面阻抗，并延长电芯的使用寿命，当采用多孔的可透气薄膜将
该气体吸附剂封装，置于电芯内部顶封空间时，该结构简单且易于产业化生产制造。在该气体吸附剂的作用下，本申请的二次电池的使用寿命得到了延长。本申请的二次电池的制备方法有助于高效的获得具有较长使用寿命的二次电池。本申请的装置包括本申请提供的二次电池，因而至少具有与所述二次电池相同的优势。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据附图获得其他的附图。
图1是二次电池的一实施方式的示意图。
图2是图1的分解图。
图3是电池模块的一实施方式的示意图。
图4是电池包的一实施方式的示意图。
图5是图4的分解图。
图6是二次电池用作电源的装置的一实施方式的示意图。
具体实施方式
为使本申请实施例的目的、技术方案和优点更加清楚，下面将对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
本申请第一方面提供一种气体吸附剂，其包括亚铜离子化合物和多孔材料。
所述气体吸附剂的气体吸附速率为0.4-1mmol/h，优选为0.7-1mmol/h。
亚铜离子化合物在气体吸附剂中的贡献在于提供亚铜离子，亚铜离子能与电芯内部气压增大的主要气体CO发生络合反应，将产生的主要气体CO消耗掉，多孔材料的作用主要在于提供适当孔径的微孔负载基体，以实现符合需求的高气体吸附剂比表面积，捕获和吸附CO、CO 2等主要气体。亚铜离子和CO发生络合反应的原理为：CO的C上有一对孤对电子，铜离子失去一个电子形成亚铜离子之后，4s轨道变空，C上的孤对电子占用了亚铜离子的4s空轨道，两者形成络合。亚铜离子化合物和多孔材料的选择和级配需满足一定的气体吸附速率要求，从而降低电芯内部产生的气压，以达到减少电芯鼓胀和界面阻抗的目的，延长电芯的使用寿命。
进一步地，引入亚铜离子主活性组分的前驱体时，应考虑熔点不会过高，制备相对容易，且化合物相对稳定，因此，采用亚铜离子的含氧酸盐或无机盐。优选地，所述亚铜离子化合物选自氧化亚铜、硫化亚铜、羧酸亚铜、硫酸亚铜、碳酸亚铜和硝酸亚铜中的一种或几种。
优选地，所述多孔材料选自A型、Y型、X型、ZSM型分子筛和磷酸铝分子筛中的一种或几种。分子筛为目前比表面积大且成本较低的多孔材料。
优选地，所述多孔材料的孔径为
Figure PCTCN2020083633-appb-000001
优选为
Figure PCTCN2020083633-appb-000002
此孔径范围允许CO分子进入多孔材料，且可最大程度避免电解液溶剂分子进入多孔材料。当多孔材料的孔径选择不当(超出
Figure PCTCN2020083633-appb-000003
范围之外)时，虽然也能一定程度上达到本申请的目的，但是其性能不够突出，这是因为电解液的溶剂分子会不断被多孔材料吸收而导致其饱和，从而失去CO和CO 2的捕捉能力，因此需要特别注意高比表面积多孔材料的选择或封闭薄膜的选择。
优选地，所述多孔材料的比表面积为400-1000m 2/g，优选为800-1000m 2/g。比表面积越大，表面可分散的亚铜化合物越多，则气体吸收效果越佳。
优选地，所述亚铜离子化合物与多孔材料的重量比为1:10-1:1，优选为1:4-1:2。所述亚铜离子化合物与所述多孔材料的重量比对于本申请目的的有效实现非常重要，如果两者比例不当，虽然可以实现本申请的目的，但对于气体的吸收效果会存在一定的影响，这是因为亚铜离子化合物与多孔材料的重量比过高则亚铜离子化合物过多，盈余的部分将无法分布在多孔材料表面，这一部分将无法有效地吸收CO；如亚铜离子化合物与多孔材料的重量比过低，则多孔材料过多，将有一部分多孔材料的表面未分布亚铜离子化合物，这一部分多孔材料将无法有效地发挥作用。
优选地，以电芯标称容量每1Ah为基准，所述亚铜离子化合物的总用量为6×10 -6-6×10 -5mol，优选为8×10 -6-2×10 -5mol。电池内气体的产生与电芯的容量相关，因而所述亚铜离子化合物的总用量需要控制在一定的范围内，才能达到兼具有效吸收气体及合理控制电芯重量的双重性能。
在具体实施过程中，本发明的气体吸附剂通过包括以下过程的方法制备得到：在隔绝水氧的环境下，将所述亚铜离子化合物与多孔材料混合并搅拌，随后将所述亚铜离子化合物熔融，得到所述气体吸附剂。
本申请第二方面是提供一种制备上述气体吸附剂的方法，包括：在隔绝水氧的环境下，将所述亚铜离子化合物与多孔材料混合并搅拌，随后将所述亚铜离子化合物熔融，得到所述气体吸附剂。
本申请的第三方面提供一种二次电池，其包括本申请第一方面所述的气体吸附剂。
本申请的二次电池是指能够反复充放电循环使用的电池，包括但不限于锂离子电池、钠离子电池等。
优选地，将本申请第一方面所述气体吸附剂封装进多孔可透气薄膜中，并置于二次电池的电芯内；更优选地，置于二次电池的电芯内顶封空间。
优选地，所述多孔可透气薄膜为微孔隔膜、织造膜、无纺布膜、纤维纸、碾压膜及复合膜中的一种或几种。这些薄膜成本低，厚度与孔径比较合适，可制造性强，且强度可满足要求。
优选地，所述多孔可透气薄膜的孔径为
Figure PCTCN2020083633-appb-000004
优选为
Figure PCTCN2020083633-appb-000005
该多孔可透气薄膜的孔径允许CO分子通过薄膜，且可最大程度避免电解液溶剂分子透过薄膜。电解液的溶剂分子会不断被多孔可透气薄膜吸收而导致其饱和，从而失去CO和CO 2的捕捉能力，因此需要特别注意高比表面积多孔可透气薄膜的选择或封闭薄膜的选择。
本申请的二次电池还包括正极极片、负极极片、隔离膜及电解质。在电池充放电过程中，活性离子在正极极片和负极极片之间往返嵌入和脱出。隔离膜设置在正极极片和负极极片之间，起到隔离的作用。电解质在正极极片和负极极片之间起到传导离子的作用。除了使用了本申请第一方面的气体吸附剂外，本申请的二次电池的构造和制备方法本身是公知的。本申请的技术人员可以根据应用需求选择合适的材料来制备上述的正极极片、负极极片、隔离膜及电解质。
本申请对二次电池的形状没有特别的限制，其可以是圆柱形、方形或其他任意的形状。如图1是作为一个示例的方形结构的二次电池5。
在一些实施例中，二次电池可包括外包装，用于封装正极极片、负极极片、隔离膜和电解液。
在一些实施例中，二次电池的外包装可以是软包，例如袋式软包。软包的材质可以是塑料，如可包括聚丙烯PP、聚对苯二甲酸丁二醇酯PBT、聚丁二酸丁二醇酯PBS等中的一种或几种。二次电池的外包装也可以是硬壳，例如硬塑料壳、铝壳、钢壳等。
在一些实施例中，参照图2，外包装可包括壳体51和盖板53。其中，壳体51可包括底板和连接于底板上的侧板，底板和侧板围合形成容纳腔。壳体51具有与容纳腔连通的开口，盖板53能够盖设于所述开口，以封闭所述容纳腔。
正极极片、负极极片和隔离膜可经卷绕工艺或叠片工艺形成电芯52。电芯52封装于所述容纳腔。电解液浸润于电芯52中。
二次电池5所含电芯52的数量可以为一个或几个，可根据需求来调节。
在一些实施例中，二次电池可以组装成电池模块，电池模块所含二次电池的数量可以为多个，具体数量可根据电池模块的应用和容量来调节。
图3是作为一个示例的电池模块4。参照图3，在电池模块4中，多个二次电池5可以是沿电池模块4的长度方向依次排列设置。当然，也可以按照其他任意的方式进行排布。进一步可以通过紧固件将该多个二次电池5进行固定。
可选地，电池模块4还可以包括具有容纳空间的外壳，多个二次电池5容纳于该容纳空间。
在一些实施例中，上述电池模块还可以组装成电池包，电池包所含电池模块的数量可以根据电池包的应用和容量进行调节。
图4和图5是作为一个示例的电池包1。参照图4和图5，在电池包1中可以包括电池箱和设置于电池箱中的多个电池模块4。电池箱包括上箱体2和下箱体3，上箱体2能够盖设于下箱体3，并形成用于容纳电池模块4的封闭空间。多个电池模块4可以按照任意的方式排布于电池箱中。
本申请的第四方面提供一种二次电池的制备方法，包括将第一方面的气体吸附剂封装进多孔可透气薄膜中，并置于二次电池的电芯内的步骤。优选 地，包括将第一方面的气体吸附剂封装进多孔可透气薄膜中，并置于二次电池的电芯内顶封空间的步骤。
本申请的第五方面提供一种装置，所述装置包括本申请第三方面所述的二次电池。所述二次电池可以用作所述装置的电源，也可以作为所述装置的能量存储单元。所述装置可以但不限于是移动设备(例如手机、笔记本电脑等)、电动车辆(例如纯电动车、混合动力电动车、插电式混合动力电动车、电动自行车、电动踏板车、电动高尔夫球车、电动卡车等)、电气列车、船舶及卫星、储能系统等。
所述装置可根据其使用需求来选择二次电池、电池模块或电池包。
图6是作为一个示例的装置。该装置为纯电动车、混合动力电动车、或插电式混合动力电动车等。为了满足该装置对电池的高功率和高能量密度的需求，可以采用电池包或电池模块。
作为另一个示例的装置可以是手机、平板电脑、笔记本电脑等。该装置通常要求轻薄化，可以采用二次电池作为电源。
为详细说明技术方案的技术内容、构造特征、所实现目的及效果，以下结合具体实施例详予说明。应理解，这些实施例仅用于说明本申请而不用于限制本申请的范围。因为在本申请公开内容的范围内进行各种修改和变化对本领域技术人员来说是明显的。实施例中使用的所有试剂都可商购获得或是按照常规方法进行合成获得，并且可直接使用而无需进一步处理，以及实施例中使用的仪器均可商购获得。
实施例1-14和对比例1-2的电池均按照下述方法进行制备。
(1)正极极片的制备
将正极活性材料LiNi 1/3Co 1/3Mn 1/3O 2、导电剂Super-P、粘结剂聚偏氟乙烯(PVDF)按质量比94:3:3进行混合，加入溶剂N-甲基吡咯烷酮(NMP)，在真空搅拌机作用下搅拌至体系呈均一状，获得正极浆料；将正极浆料均匀涂覆在正极集流体铝箔的两个表面上，室温晾干后转移至烘箱继续干燥，然后经过冷压、分切，得到正极极片。
(2)负极极片的制备
将负极活性材料、导电剂Super P、增稠剂羧甲基纤维素钠(CMC)、粘结剂丁苯橡胶乳液(SBR)按照质量比96:1:1:2进行混合，加入至溶剂去离子 水中，在真空搅拌机作用下搅拌均匀，获得负极浆料；将负极浆料均匀涂覆在负极集流体铜箔上，室温晾干后转移至烘箱继续干燥，然后经过冷压、切边、裁片、分条，移至真空中的烘箱，得到负极极片。
(3)电解液的制备
将碳酸乙烯酯(EC)、碳酸甲乙酯(EMC)按照按体积比3:7进行混合得到有机溶剂，接着将充分干燥的LiPF 6溶解于混合后的有机溶剂中，配制成浓度1mol/L的电解液。
(4)隔离膜的制备
选PE/PP/PE三层多孔聚合薄膜作为隔离膜。
(5)气体吸附剂的制备
将表1所示亚铜离子化合物与多孔材料在无CO、CO 2、O 2、H 2O和其它氧化性物质存在的环境下进行混合，并在密封容器中隔绝水分与氧气进行搅拌1-24h，得到均匀的混合粉末，在高温(80-750℃)下进行加热1-24h处理，亚铜离子化合物粉末在高温下熔化，并均匀渗入高比表面的多孔材料内部和表面，即得到所述气体吸附剂。
(6)二次电池的制备
将上述正极极片、隔离膜、负极极片按顺序叠好，使隔离膜处于正、负极极片之间起到隔离的作用，然后卷绕得到裸电芯；将表1所示参数按照(5)制备得到的气体吸附剂封装进表1所示的不同孔径的微孔隔膜中，并置于二次电池的电芯内顶封空间，将裸电芯置于外包装壳中，干燥后注入电解液，经过真空封装、静置、化成、整形等工序，获得二次电池。
以下说明含有气体吸附剂的二次电池的电芯内部气压和气体吸附速率的实验测量方法。
(1)电芯内部气压测量方法
在电芯顶盖上连接一个压力计，计数清零后，将电芯放置于温度为70°的高低温箱中，静置，每日读取压力计读数，直到压力计读数显示为0.35MPa为止，记录达到0.35MPa所用的天数。
(2)气体吸附速率测量方法
在密闭空间中放置5g该气体吸附剂，向密闭空间内充一氧化碳气体CO至正压0.1MPa，静置2～8h，实时监控气压，最终计算得到吸附速率。
表1气体吸附剂及其二次电池电芯的相关参数
Figure PCTCN2020083633-appb-000006
从表1中数据可知，实施例1-5说明延长电芯高温存储产气寿命的效果与亚铜离子化合物与多孔材料的重量比相关，亚铜离子化合物与多孔材料的重量比在1:4-1:2范围内效果最佳。亚铜离子化合物与多孔材料的重量比过高即亚铜离子化合物过多，盈余的部分将无法分布在多孔材料表面，这一部分将无法有效地吸收CO，如亚铜离子化合物与多孔材料的重量比过低即多孔材料过多，将有一部分多孔材料的表面未分布亚铜离子化合物，这一部分多孔材料将无法有效地发挥作用。
实施例3、6说明延长电芯高温存储产气寿命的效果与多孔材料的类型相关，A型相对X型效果更优。
实施例6、7说明延长电芯高温存储产气寿命的效果与亚铜离子化合物种类有关，硫化亚铜相对氯化亚铜效果更优。
实施例5、8、9说明延长电芯高温存储产气寿命的效果与多孔材料的孔径有关，
Figure PCTCN2020083633-appb-000007
范围内效果最优，该孔径可允许CO分子进入多孔材料，且可最大程度避免电解液溶剂分子进入多孔材料，如电解液的溶剂分子过多地被多孔材料吸收而导致其饱和，将使得多孔材料失去CO和CO 2的捕捉能力。
实施例8、10、11说明延长电芯高温存储产气寿命的效果与多孔可透气薄的孔径有关，多孔可透气薄膜孔径在
Figure PCTCN2020083633-appb-000008
范围内效果最优，该孔径可允许CO分子透过薄膜，且可最大程度避免电解液溶剂分子透过薄膜，如电解液的溶剂分子过多地透过薄膜从而被多孔可透气薄膜吸收而导致其饱和，将使得多孔可透气薄膜失去CO和CO 2的捕捉能力。
实施例10、12-14说明延长电芯高温存储产气寿命的效果与亚铜离子化合物的总用量与电芯容量的比值相关，亚铜离子化合物的总用量与电芯容量的比值在8×10 -6-2×10 -5范围内效果最佳，过少则无法完全地吸收气体，过多则吸附剂有盈余，使电芯能量密度降低。
对比例中，无亚铜离子化合物或无多孔材料的吸附剂无延长电芯高温存储产气寿命的效果。
需要说明的是，尽管在本文中已经对上述各实施例进行了描述，但并非因此限制本申请的专利保护范围。因此，基于本申请的创新理念，对本文所述实施例进行的变更和修改，或利用本申请说明书内容所作的等效结构或等效流程变换，直接或间接地将以上技术方案运用在其他相关的技术领域，均包括在本申请的专利保护范围之内。

Claims (23)

  1. 一种气体吸附剂，包括亚铜离子化合物和多孔材料。
  2. 根据权利要求1所述的气体吸附剂，其中，所述气体吸附速率为0.4-1mmol/h。
  3. 根据权利要求2所述的气体吸附剂，其中，所述气体吸附速率为0.7-1mmol/h。
  4. 根据权利要求1-3任一项所述的气体吸附剂，其中，所述亚铜离子化合物选自氧化亚铜、硫化亚铜、羧酸亚铜、硫酸亚铜、碳酸亚铜和硝酸亚铜中的一种或几种。
  5. 根据权利要求1-4任一项所述的气体吸附剂，其中，所述多孔材料选自A型、Y型、X型、ZSM型分子筛和磷酸铝分子筛中的一种或几种。
  6. 根据权利要求1-5任一项所述的气体吸附剂，其中，所述多孔材料的孔径为
    Figure PCTCN2020083633-appb-100001
  7. 根据权利要求6所述的气体吸附剂，其中，所述多孔材料的孔径为
    Figure PCTCN2020083633-appb-100002
  8. 根据权利要求1-7任一项所述的气体吸附剂，其中，所述多孔材料的比表面积为400-1000m 2/g。
  9. 根据权利要求8所述的气体吸附剂，其中，所述多孔材料的比表面积为800-1000m 2/g。
  10. 根据权利要求1-9任一项所述的气体吸附剂，其中，所述亚铜离子化合物与多孔材料的重量比为1:10-1:1。
  11. 根据权利要求10所述的气体吸附剂，其中，所述亚铜离子化合物与多孔材料的重量比为1:4-1:2。
  12. 根据权利要求1-11任一项所述的气体吸附剂，其中，以电芯标称容量每1Ah为基准，所述亚铜离子化合物的总用量为6×10 -6-6×10 -5mol。
  13. 根据权利要求12所述的气体吸附剂，其中，以电芯标称容量每1Ah为基准，所述亚铜离子化合物的总用量为8×10 -6-2×10 -5mol。
  14. 根据权利要求1-13任一项所述的气体吸附剂，其中，所述气体吸附剂通过包括以下过程的方法制备得到：
    在隔绝水氧的环境下，将所述亚铜离子化合物与多孔材料混合并搅拌， 随后将所述亚铜离子化合物熔融，得到所述气体吸附剂。
  15. 一种权利要求1-14任一项所述的气体吸附剂的制备方法：
    在隔绝水氧的环境下，将所述亚铜离子化合物与多孔材料混合并搅拌，随后将所述亚铜离子化合物熔融，得到所述气体吸附剂。
  16. 一种二次电池，其中，所述二次电池包括权利要求1-14任一项所述的气体吸附剂。
  17. 根据权利要求16所述的二次电池，其中，将所述气体吸附剂封装进多孔可透气薄膜中，并置于二次电池的电芯内。
  18. 根据权利要求17所述的二次电池，其中，将所述气体吸附剂封装进多孔可透气薄膜中，并置于二次电池的电芯内顶封空间。
  19. 根据权利要求17-18任一项所述的二次电池，其中，所述多孔可透气薄膜为微孔隔膜、织造膜、无纺布膜、纤维纸、碾压膜及复合膜中的一种或几种。
  20. 根据权利要求17-19任一项所述的二次电池，其中，所述多孔可透气薄膜的孔径为
    Figure PCTCN2020083633-appb-100003
  21. 根据权利要求20所述的二次电池，其中，所述多孔可透气薄膜的孔径为
    Figure PCTCN2020083633-appb-100004
  22. 一种权利要求16-21任一项所述的二次电池的制备方法，其中，包括以下步骤：将权利要求1-14任一项所述的气体吸附剂封装进多孔可透气薄膜中，并置于二次电池的电芯内。
  23. 一种装置，其中，所述装置包括权利要求16-21任一项所述的二次电池。
PCT/CN2020/083633 2019-05-23 2020-04-08 一种气体吸附剂、二次电池及装置 Ceased WO2020233264A1 (zh)

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