WO2023184784A1 - Batterie secondaire, module de batterie, bloc-batterie et dispositif électrique - Google Patents

Batterie secondaire, module de batterie, bloc-batterie et dispositif électrique Download PDF

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Publication number
WO2023184784A1
WO2023184784A1 PCT/CN2022/105357 CN2022105357W WO2023184784A1 WO 2023184784 A1 WO2023184784 A1 WO 2023184784A1 CN 2022105357 W CN2022105357 W CN 2022105357W WO 2023184784 A1 WO2023184784 A1 WO 2023184784A1
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thermal expansion
material layer
active material
negative
negative thermal
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PCT/CN2022/105357
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English (en)
Chinese (zh)
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王文轩
王国宝
曹娇
刘东旭
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宁德时代新能源科技股份有限公司
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Publication of WO2023184784A1 publication Critical patent/WO2023184784A1/fr

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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
    • H01M10/05—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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/202—Casings or frames around the primary casing of a single cell or a single battery
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application relates to the technical field of lithium batteries, and in particular to a secondary battery, a battery module, a battery pack and an electrical device.
  • secondary batteries are widely used in energy storage power systems such as hydropower, thermal power, wind power and solar power stations, as well as power tools, electric bicycles, Electric motorcycles, electric vehicles, military equipment, aerospace and other fields. Since secondary batteries have a wide range of applications and a wide temperature range when used, higher requirements are placed on their electrochemical performance at low temperatures.
  • This application was made in view of the above-mentioned issues, and its purpose is to provide a secondary battery, battery module, battery pack and electrical device that can enhance the resilience of the pole piece of the secondary battery at low temperatures and improve the performance of the secondary battery. Low temperature operating conditions.
  • a first aspect of the present application provides a secondary battery, including a pole piece and an electrolyte, wherein the pole piece and/or the electrolyte contains a negative thermal expansion material, and the negative thermal expansion material is included at -60°C.
  • a secondary battery including a pole piece and an electrolyte, wherein the pole piece and/or the electrolyte contains a negative thermal expansion material, and the negative thermal expansion material is included at -60°C.
  • the present application adds the above-mentioned negative thermal expansion material to the pole pieces and/or the electrolyte of the secondary battery, so that the pole pieces can still maintain a high degree of rebound expansion at low temperatures, thereby improving the performance of the electrolyte in low-temperature environments.
  • the fluidity in the battery is improved, thereby improving the lithium deposition of the pole pieces and improving the operating conditions of the battery cells in low-temperature environments.
  • the negative thermal expansion material is selected from the group consisting of artificial hollow fibers, antimony, bismuth, gallium, nickel sulfide, bronze, rubber, zirconium tungstate, scandium fluoride, zinc cyanide (Zn(CN) 2 ), At least one of cadmium cyanide (Cd(CN) 2 ) and gallium ruthenium oxide.
  • the negative thermal expansion material includes gallium ruthenium oxide.
  • the deformation degree of the pole piece between -60°C and 100°C can be effectively adjusted, and the deformation amount can be kept in a low range (for example, within 10%), thereby making the battery core Within this temperature range, normal throughput of the electrolyte can still be carried out, improving the fluidity of the electrolyte, accelerating the transmission rate of active ions (such as lithium ions), and improving the lithium precipitation of the pole pieces, thus improving the operating conditions of the battery cell. .
  • the pole piece includes:
  • An active material layer is provided on at least one side of the current collector, and the active material layer includes the negative thermal expansion material.
  • the rebound expansion of the pole piece at low temperatures can be improved, allowing the battery core to maintain a certain degree of volume expansion and contraction, and improving the fluidity of the electrolyte in low temperature environments.
  • the pole piece includes a positive pole piece and/or a negative pole piece
  • the active material layer includes a negative active material layer and/or a positive active material layer
  • the negative active material layer and/or the The negative thermal expansion material is included in the positive active material layer.
  • the resilience of the negative electrode piece and/or the positive electrode piece at low temperatures can be effectively improved.
  • the mass percentage of the negative thermal expansion material is 0.01% to 6%, preferably 0.8% to 1.85%.
  • the mass percentage of the negative thermal expansion material is 0.01% to 6%, preferably 1% to 2.2%.
  • the mass percentage of the negative thermal expansion material in the negative active material layer and/or the positive active material layer within an appropriate range, it can be ensured that the negative electrode piece and/or the positive electrode piece still have excellent rebound performance at low temperatures, thus It greatly improves the fluidity of the electrolyte and significantly and effectively improves the lithium precipitation of the pole pieces, while also ensuring the complete uniformity of the pole pieces.
  • the active material layer includes:
  • a negative thermal expansion material layer is provided on the side of the active material layer close to the current collector and/or the side of the active material layer away from the current collector, wherein the negative thermal expansion material layer contains the negative thermal expansion material layer. Thermal expansion materials.
  • the negative thermal expansion material layer is provided as a separate film layer, which is conducive to regulating the degree of rebound of the negative electrode piece and/or the positive electrode piece at low temperatures by regulating the thickness of the film layer, which is more conducive to Improve the lithium deposition situation of the pole pieces.
  • the thickness of the negative thermal expansion material layer is 0.1 ⁇ m to 50 ⁇ m, preferably 5 ⁇ m to 45 ⁇ m.
  • the thickness of the negative thermal expansion material layer is within a suitable range, which is conducive to significantly improving the resilience of the pole piece at low temperatures, greatly improving the fluidity of the electrolyte, reducing the transfer resistance of charges and active ions, thereby effectively improving the pole piece The situation of lithium evolution.
  • the mass percentage of the negative thermal expansion material is 0.01% to 5%, preferably 2% to 3.5%.
  • the mass percentage of negative thermal expansion materials in the electrolyte is within an appropriate range, which can greatly increase the freezing point of the electrolyte, allowing the electrolyte to maintain very good fluidity in low-temperature environments, thereby accelerating the release of active ions (such as lithium ions)
  • the transmission rate can reduce the concentration gradient of lithium ions in the directions perpendicular to and parallel to the pole piece, and improve the lithium deposition of the pole piece.
  • a second aspect of the present application provides a battery module including the secondary battery of the first aspect of the present application.
  • a third aspect of the present application provides a battery pack, including the battery module of the second aspect of the present application.
  • a fourth aspect of the present application provides an electrical device, including at least one selected from the secondary battery of the first aspect of the present application, the battery module of the second aspect of the present application, or the battery pack of the third aspect of the present application. kind.
  • the battery modules, battery packs and electrical devices of the present application include the secondary battery provided by the present application, and thus have at least the same advantages as the secondary battery.
  • Figure 1 is a test chart of interface lithium evolution of the negative electrode sheet of Example 1 at -10°C.
  • Figure 2 is a test chart of the interface lithium evolution of the negative electrode sheet of Comparative Example 1 at -10°C.
  • Figure 3 is a comparison chart of the resilience test results of the negative electrode piece in Example 1 and Comparative Example 1.
  • FIG. 4 is a schematic diagram of a secondary battery according to an embodiment of the present application.
  • FIG. 5 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 4 .
  • Figure 6 is a schematic diagram of a battery module according to an embodiment of the present application.
  • Figure 7 is a schematic diagram of a battery pack according to an embodiment of the present application.
  • FIG. 8 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG. 7 .
  • FIG. 9 is a schematic diagram of a power consumption device using a secondary battery as a power source according to an embodiment of the present application.
  • Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
  • a certain parameter is an integer ⁇ 2
  • the method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
  • step (c) means that step (c) may be added to the method in any order.
  • the method may include steps (a), (b) and (c). , may also include steps (a), (c) and (b), may also include steps (c), (a) and (b), etc.
  • condition "A or B” is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; Or both A and B are true (or exist).
  • both the positive and negative electrode plates expand to a certain extent, causing the battery core to also expand and contract to a certain extent.
  • the core will repeatedly "suck in” and “spit out” the electrolyte like “breathing”, so at different times, the infiltration of the electrolyte in the battery core will change in real time, so there are usually lithium ions in the direction perpendicular to the pole piece. Concentration gradient.
  • the electrolyte in the electrode part also has a process of drying and rewetting.
  • the inventor found that when the secondary battery is in a low-temperature environment, due to the influence of the external environment, the volume expansion and contraction of the positive and negative electrode plates will be affected to a certain extent, causing the "breathing" amplitude of the battery core to weaken, thereby causing To a certain extent, the fluidity of the electrolyte becomes weaker, and the lithium ion concentration gradient increases in both directions perpendicular to the pole piece and parallel to the pole piece, which will aggravate the lithium precipitation of the pole piece.
  • this application provides a secondary battery mainly from the perspective of the deformation degree of the positive and negative electrode plates in a low-temperature environment and the fluidity of the electrolyte.
  • the secondary battery includes the electrode plates and the electrolyte, wherein , the pole piece and/or the electrolyte contains a negative thermal expansion material.
  • the fluidity of the electrolyte in low temperature environments can be improved, and the degree of deformation of the pole pieces and the "breathing" amplitude of the battery core can be reduced. Large changes occur due to temperature changes, thereby improving the operating conditions of the battery core at low temperatures.
  • the present application proposes a secondary battery including a pole piece and an electrolyte, wherein the pole piece and/or the electrolyte contains a negative thermal expansion material (NTE), and the negative thermal expansion material (NTE) is included in the negative thermal expansion material.
  • Thermal expansion materials include at least one of metal elements, alloys, metal oxides, metal sulfides, cyanides, fluorides, polymer compounds and metal-organic frameworks that have a negative thermal expansion coefficient between -60°C and 100°C.
  • negative thermal expansion material refers to a type of material whose length or volume shrinks as the temperature increases; "having a negative thermal expansion coefficient between -60°C ⁇ 100°C” means that between -60°C and 100°C In at least one temperature range (for example, -60°C ⁇ 0°C), the average linear expansion coefficient or volume expansion coefficient is negative.
  • the average linear expansion coefficient or volume expansion coefficient can be measured by the following method.
  • the negative thermal expansion material can weaken the shrinkage deformation of the pole piece due to the decrease in temperature, so that the pole piece can still maintain a high degree of rebound expansion, so the battery core can also maintain a certain degree of volume expansion and contraction, which can Maintain normal repeated "sucking in” and “spitting out” of the electrolyte to improve the fluidity of the electrolyte in low-temperature environments, thereby improving the lithium precipitation of the pole pieces and improving the operating conditions of the battery cells in low-temperature environments.
  • this application can increase the freezing point of the electrolyte by adding the above-mentioned negative thermal expansion material to the electrolyte of the secondary battery, so that the electrolyte still maintains good fluidity in a low-temperature environment, thereby speeding up the activity of active ions (such as lithium).
  • active ions such as lithium
  • the transmission rate of ions can improve the lithium deposition of the pole pieces, which can also improve the operating conditions of the battery cells in low-temperature environments.
  • the negative thermal expansion material is selected from the group consisting of artificial hollow fibers, antimony, bismuth, gallium, nickel sulfide, bronze, rubber, zirconium tungstate, scandium fluoride, zinc cyanide (Zn(CN) 2 ), At least one of cadmium cyanide (Cd(CN) 2 ) and gallium ruthenium oxide (Ga 2 RuO 4 ).
  • the negative thermal expansion material includes gallium ruthenium oxide.
  • the deformation degree of the pole piece between -60°C and 100°C can be effectively adjusted, and the deformation amount can be kept in a low range (for example, within 10%).
  • the battery core can still carry out normal throughput of the electrolyte within this temperature range, improve the fluidity of the electrolyte, accelerate the transmission rate of active ions (such as lithium ions), and improve the lithium precipitation of the pole pieces, thereby improving the battery core operating conditions.
  • gallium ruthenium oxide has a better effect on improving the deformation of the pole piece, and can better improve the fluidity of the electrolyte, thereby improving the battery core's temperature between -60°C and 100°C. operating conditions during the period.
  • the pole piece includes: a current collector, and an active material layer disposed on at least one side of the current collector, where the active material layer includes the negative thermal expansion material.
  • the rebound expansion property of the pole piece at low temperatures can be improved, allowing the battery core to maintain a certain degree of volume expansion and contraction, and improving the flow of electrolyte in low temperature environments. properties, reducing the transfer resistance of charges and active ions, thereby improving the lithium precipitation of the pole pieces and improving the operating conditions of the battery cells.
  • the pole piece includes a positive pole piece and/or a negative pole piece
  • the active material layer includes a negative active material layer and/or a positive active material layer
  • the negative active material layer and/or the The negative thermal expansion material is included in the positive active material layer.
  • the negative thermal expansion material is included in the negative active material layer and/or the positive active material layer, which is equivalent to adding the negative thermal expansion material as an additive to the negative active material and/or the positive active material, and then containing the negative thermal expansion material.
  • the negative active material and/or the positive active material of the negative thermal expansion material is coated on at least one side of the current collector as a separate active material layer.
  • the mass percentage of the negative thermal expansion material is 0.01% to 6%, for example, the mass percentage of the negative thermal expansion material is 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% or within the range of any of the above values.
  • the mass percentage of the negative thermal expansion material is 0.8% to 1.85%.
  • the mass percentage of the negative thermal expansion material is 0.01% to 6%, for example, the mass percentage of the negative thermal expansion material is 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6% or within the range of any of the above values.
  • the mass percentage of the negative thermal expansion material is 1% to 2.2%.
  • the mass percentage of the negative thermal expansion material in the negative active material layer and/or the positive active material layer within an appropriate range, it can be ensured that the negative electrode piece and/or the positive electrode piece still have excellent performance at low temperatures.
  • the rebound performance can greatly improve the fluidity of the electrolyte, significantly and effectively improve the lithium precipitation of the pole pieces, and at the same time ensure the complete uniformity of the pole pieces.
  • the active material layer includes: an active material layer and a negative thermal expansion material layer.
  • the negative thermal expansion material layer is disposed on a side of the active material layer close to the current collector and/or the active material layer. A side of the layer away from the current collector, wherein the negative thermal expansion material is included in the negative thermal expansion material layer.
  • the negative thermal expansion material layer is disposed on the side of the active material layer close to the current collector, which is equivalent to disposing the negative thermal expansion material layer between the active material layer and the current collector.
  • the negative thermal expansion material layer is disposed on the side of the active material layer away from the current collector, it is equivalent to disposing the active material layer between the negative thermal expansion material layer and the current collector.
  • the rebound expansion properties of the negative electrode piece and/or the positive electrode piece at low temperatures can be improved.
  • This further improves the volume expansion and contraction of the battery core, allowing the battery core to maintain normal "sucking in” and “spitting out” electrolyte at low temperatures, thus improving the fluidity of the electrolyte in low temperature environments, thereby improving the analysis of the pole pieces.
  • Lithium state improves the operating conditions of batteries in low-temperature environments.
  • arranging the negative thermal expansion material layer as a separate film layer is also conducive to regulating the degree of rebound of the negative electrode piece and/or the positive electrode piece at low temperatures by regulating the thickness of the film layer, which is more conducive to the control of the electrode. Improve the lithium deposition situation of tablets.
  • the thickness of the negative thermal expansion material layer is 0.1 ⁇ m to 50 ⁇ m.
  • the thickness of the negative thermal expansion material layer is 0.5 ⁇ m, 1 ⁇ m, 5 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m. , 40 ⁇ m, 45 ⁇ m, 50 ⁇ m or within the range of any of the above values.
  • the thickness of the negative thermal expansion material layer is 5 ⁇ m to 45 ⁇ m.
  • the thickness of the negative thermal expansion material layer is within a suitable range, which is conducive to significantly improving the resilience of the pole piece at low temperatures, greatly improving the fluidity of the electrolyte, and reducing the transfer resistance of charges and active ions, thus Effectively improve the lithium precipitation situation of the pole piece.
  • the mass percentage of the negative thermal expansion material is 0.01% to 5%.
  • the mass percentage of the negative thermal expansion material is 0.05%, 0.1% , 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% or within the range of any of the above values.
  • the mass percentage of the negative thermal expansion material is 2% to 3.5%.
  • the mass percentage of negative thermal expansion materials in the electrolyte is within an appropriate range, which can greatly increase the freezing point of the electrolyte, so that the electrolyte still maintains very good fluidity in a low-temperature environment, thereby accelerating the activation of active ions (such as the transmission rate of lithium ions), reducing the concentration gradient of lithium ions in the direction perpendicular to the pole piece and parallel to the pole piece, improving the lithium precipitation situation of the pole piece, thus greatly improving the operating conditions of the battery cell in a low-temperature environment .
  • the negative thermal expansion material can be provided in the negative electrode sheet, the positive electrode sheet, the electrolyte, or any combination of the three of the secondary battery.
  • the negative thermal expansion material can be added to the negative active material layer as an additive, or can be provided as a separate film layer on one side of the negative active material layer, or both methods can exist at the same time.
  • the negative thermal expansion material can be added to the cathode active material layer as an additive, or can be provided as a separate film layer on one side of the cathode active material layer, or both methods can exist at the same time. . Any of the above arrangements or combinations thereof can be considered to fall within the protection scope of this application.
  • the secondary battery of the present application includes a lithium-ion secondary battery or a sodium-ion secondary battery.
  • the secondary battery includes a separator in addition to a positive electrode sheet, a negative electrode sheet, and an electrolyte.
  • a separator in addition to a positive electrode sheet, a negative electrode sheet, and an electrolyte.
  • active ions are inserted and detached back and forth between the positive and negative electrodes.
  • the electrolyte plays a role in conducting ions between the positive and negative electrodes.
  • the isolation film is placed between the positive electrode piece and the negative electrode piece. It mainly prevents the positive and negative electrodes from short-circuiting and allows ions to pass through.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector.
  • the positive electrode active material layer includes a positive electrode active material layer, and the positive electrode active material layer includes a positive electrode active material.
  • the positive electrode current collector has two surfaces facing each other in its own thickness direction, and the positive electrode active material layer is disposed on any one or both of the two opposite surfaces of the positive electrode current collector.
  • the positive electrode current collector may be a metal foil or a composite current collector.
  • the metal foil aluminum foil can be used.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer.
  • the composite current collector can be formed by forming metal materials (aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the cathode active material may be a cathode active material known in the art for batteries.
  • the cathode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate, a lithium transition metal oxide, and their respective modified compounds.
  • the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials of batteries can also be used. Only one type of these positive electrode active materials may be used alone, or two or more types may be used in combination.
  • lithium transition metal oxides may include, but are not limited to, lithium cobalt oxides (such as LiCoO 2 ), lithium nickel oxides (such as LiNiO 2 ), lithium manganese oxides (such as LiMnO 2 , LiMn 2 O 4 ), lithium Nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (such as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (also referred to as NCM333), LiNi 0.5 Co 0.2 Mn 0.3 O 2 (can also be abbreviated to NCM523), LiNi 0.5 Co0.
  • lithium cobalt oxides such as LiCoO 2
  • lithium nickel oxides such as LiNiO 2
  • lithium manganese oxides such as LiMnO 2 , LiMn 2 O 4
  • Nickel cobalt oxide lithium manganese cobalt oxide
  • lithium nickel manganese oxide lithium nickel cobalt manganese oxide
  • lithium nickel cobalt manganese oxide such as
  • NCM211 25 Mn 0.25 O 2
  • LiNi 0.6 Co 0.2 Mn 0.2 O 2 can also be abbreviated to NCM622
  • LiNi0 .8 Co At least one of 0.1 Mn 0.1 O 2 (also referred to as NCM811), lithium nickel cobalt aluminum oxide (such as LiNi 0.85 Co0 .15 Al 0.05 O 2 ) and its modified compounds.
  • Lithium-containing phosphate with olivine structure examples may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), composites of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ), composites of lithium manganese phosphate and carbon , lithium iron manganese phosphate, at least one composite material of lithium iron manganese phosphate and carbon.
  • the positive active material layer optionally further includes a binder.
  • the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene At least one of ethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer and fluorine-containing acrylate resin.
  • the positive active material layer optionally further includes a conductive agent.
  • the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the positive electrode sheet can be prepared by dispersing the above-mentioned components for preparing the positive electrode sheet, such as positive active material, conductive agent, binder and any other components in a solvent (such as N -methylpyrrolidone) to form a positive electrode slurry; the positive electrode slurry is coated on the positive electrode current collector, and after drying, cold pressing and other processes, the positive electrode piece can be obtained.
  • a solvent such as N -methylpyrrolidone
  • the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector.
  • the negative electrode active material layer includes a negative electrode active material layer, and the negative electrode active material layer includes a negative electrode active material.
  • the negative electrode current collector has two opposite surfaces in its own thickness direction, and the negative electrode active material layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
  • the negative electrode current collector may be a metal foil or a composite current collector.
  • the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base material.
  • the composite current collector can be formed by forming metal materials (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
  • PP polypropylene
  • PBT polybutylene terephthalate
  • PS polystyrene
  • PE polyethylene
  • the negative active material may be a negative active material known in the art for batteries.
  • the negative active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like.
  • the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon carbon composites, silicon nitrogen composites and silicon alloys.
  • the tin-based material may be selected from at least one of elemental tin, tin oxide compounds and tin alloys.
  • the present application is not limited to these materials, and other traditional materials that can be used as battery negative electrode active materials can also be used. Only one type of these negative electrode active materials may be used alone, or two or more types may be used in combination.
  • the negative active material layer optionally further includes a binder.
  • the binder can be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), polysodium acrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), poly At least one of methacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
  • the negative active material layer optionally further includes a conductive agent.
  • the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
  • the negative active material layer optionally includes other auxiliaries, such as thickeners (such as sodium carboxymethyl cellulose (CMC-Na)) and the like.
  • auxiliaries such as thickeners (such as sodium carboxymethyl cellulose (CMC-Na)) and the like.
  • the negative electrode sheet can be prepared by dispersing the above-mentioned components for preparing the negative electrode sheet, such as negative active materials, conductive agents, binders and any other components in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode piece can be obtained.
  • a solvent such as deionized water
  • the electrolyte plays a role in conducting ions between the positive and negative electrodes. This application has no specific restrictions on the type of electrolyte and can be selected according to needs.
  • the electrolyte solution includes an electrolyte salt and a solvent.
  • the electrolyte salt may be selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluoroborate, lithium dioxaloborate, lithium difluorodioxalate phosphate and lithium tetrafluoroxalate phosphate.
  • the solvent may be selected from the group consisting of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, Butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate At least one of ester, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
  • the electrolyte optionally further includes additives.
  • additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain properties of the battery, such as additives that improve battery overcharge performance, additives that improve battery high-temperature or low-temperature performance, etc.
  • the secondary battery further includes a separator film.
  • This application has no special restrictions on the type of isolation membrane, and any well-known porous structure isolation membrane with good chemical stability and mechanical stability can be selected.
  • the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
  • the isolation film can be a single-layer film or a multi-layer composite film, with no special restrictions. When the isolation film is a multi-layer composite film, the materials of each layer can be the same or different, and there is no particular limitation.
  • the positive electrode piece, the negative electrode piece and the separator film can be made into an electrode assembly through a winding process or a lamination process.
  • the secondary battery may include an outer packaging.
  • the outer packaging can be used to package the above-mentioned electrode assembly and electrolyte.
  • the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
  • the outer packaging of the secondary battery may also be a soft bag, such as a bag-type soft bag.
  • the material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
  • FIG. 4 shows a square-structured secondary battery 5 as an example.
  • the outer package may include a housing 51 and a cover 53 .
  • the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose a receiving cavity.
  • the housing 51 has an opening communicating with the accommodation cavity, and the cover plate 53 can cover the opening to close the accommodation cavity.
  • the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 52 through a winding process or a lamination process.
  • the electrode assembly 52 is packaged in the containing cavity.
  • the electrolyte soaks into the electrode assembly 52 .
  • the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
  • secondary batteries can be assembled into battery modules, and the number of secondary batteries contained in the battery module can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery module.
  • FIG. 6 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 .
  • the plurality of secondary batteries 5 can be fixed by fasteners.
  • the battery module 4 may further include a housing having an accommodation space in which a plurality of secondary batteries 5 are accommodated.
  • the above-mentioned battery modules can also be assembled into a battery pack.
  • the number of battery modules contained in the battery pack can be one or more. Those skilled in the art can select the specific number 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 disposed in the battery box.
  • the battery box includes an upper box 2 and a lower box 3 .
  • the upper box 2 can be covered with the lower box 3 and form a closed space for accommodating the battery module 4 .
  • Multiple battery modules 4 can be arranged in the battery box in any manner.
  • the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application.
  • the secondary battery, battery module, or battery pack may be used as a power source for the electrical device, or may be used as an energy storage unit for the electrical device.
  • the electric device may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, and electric golf carts). , electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
  • a secondary battery, a battery module or a battery pack can be selected according to its usage requirements.
  • Figure 9 is an electrical device as an example.
  • the electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, etc.
  • a battery pack or battery module can be used.
  • the device may be a mobile phone, a tablet, a laptop, etc.
  • This device is usually required to be thin and light, and secondary batteries can be used as power sources.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DEC diethyl carbonate
  • FEC Fluoroethylene carbonate
  • Polypropylene film is used as the isolation film.
  • Electrode assembly Stack the positive electrode sheet, isolation film, and negative electrode sheet in order and wind them to obtain an electrode assembly. Put the electrode assembly into the outer packaging, add the above-mentioned electrolyte, and go through processes such as packaging, standing, forming, and shaping to obtain the second electrode assembly. Secondary battery.
  • Example 2 The preparation methods of Examples 2 to 4 are similar to Example 1, except that the content of Ga 2 RuO 4 powder in the negative active material layer is adjusted.
  • Examples 5 to 7 are similar to Example 1, except that Ga 2 RuO 4 is not added to the negative active material layer, but Ga 2 RuO 4 is added to the positive active material layer, and the positive active material is adjusted. The content of Ga 2 RuO 4 powder in the layer.
  • Example 5 The preparation methods of Examples 5 to 7 are similar to Example 1, except that Ga 2 RuO 4 is not added to the negative active material layer, but Ga 2 RuO 4 is applied to the negative active material layer as a separate negative thermal expansion material layer. The side closer to/away from the current collector, and the thickness of the negative thermal expansion material layer is adjusted.
  • Examples 8 to 13 are similar to Example 1, except that Ga 2 RuO 4 is not added to the negative active material layer, but Ga 2 RuO 4 powder is added to the electrolyte, and the electrolyte is adjusted. Ga 2 RuO 4 content.
  • Example 17 The preparation method of Example 17 is similar to that of Example 1, except that Ga 2 RuO 4 is added to the electrolyte solution at the same time.
  • Example 18 The preparation method of Example 18 is similar to that of Example 8, except that Ga 2 RuO 4 is added to the electrolyte solution at the same time.
  • Comparative Example 1 The preparation method of Comparative Example 1 is similar to that of Example 1, except that Ga 2 RuO 4 is not added to the negative active material layer, that is, Ga 2 RuO 4 is not added to the secondary battery.
  • the pole piece cells in Examples 1 to 18 and Comparative Example 1 were fully charged and discharged at different rates in a low temperature environment (-10°C) for a certain number of cycles; at the end of the cycle, the cells were fully charged and the interface was disassembled. , observe the lithium precipitation at the interface of the pole piece.
  • each sample can take 5 to 6 of the middle layer of the battery core.
  • Layer the electrode piece and then use an electrochemical impedance analyzer to conduct a charge transfer impedance test at low temperature (-10°C) on the electrode piece, and record the test results.

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Abstract

La présente demande concerne une batterie secondaire, un module de batterie, un bloc-batterie et un dispositif électrique. La batterie secondaire comprend une pièce polaire et un électrolyte, la pièce polaire et/ou l'électrolyte comprenant un matériau à dilatation thermique négative, et le matériau à dilatation thermique négative comprenant au moins un constituant parmi un élément métallique, un alliage, un oxyde métallique, un sulfure métallique, un cyanure, un fluorure, un composé polymère et une structure organométallique ayant un coefficient de dilatation thermique négatif compris entre -60 °C et 100 °C. La pièce polaire de la batterie secondaire selon la présente demande peut toujours maintenir une performance de rebond relativement élevée dans un environnement à basse température, de telle sorte que la batterie présente de bonnes conditions de fonctionnement à basses températures.
PCT/CN2022/105357 2022-03-31 2022-07-13 Batterie secondaire, module de batterie, bloc-batterie et dispositif électrique WO2023184784A1 (fr)

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CN202210335846.5A CN116936912A (zh) 2022-03-31 2022-03-31 二次电池、电池模块、电池包和用电装置

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015191768A (ja) * 2014-03-28 2015-11-02 トヨタ自動車株式会社 二次電池
CN105552297A (zh) * 2015-12-18 2016-05-04 力神动力电池系统有限公司 一种具有高安全性的锂离子电池
CN106654165A (zh) * 2016-11-08 2017-05-10 珠海光宇电池有限公司 一种锂离子电池极片、制备方法及锂离子电池
JP2017174648A (ja) * 2016-03-24 2017-09-28 株式会社豊田中央研究所 蓄電デバイス
CN110010897A (zh) * 2019-04-16 2019-07-12 江苏碳谷二维世界科技有限公司 一种石墨烯锂电池正极浆料、制备方法及锂电池正极极片

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015191768A (ja) * 2014-03-28 2015-11-02 トヨタ自動車株式会社 二次電池
CN105552297A (zh) * 2015-12-18 2016-05-04 力神动力电池系统有限公司 一种具有高安全性的锂离子电池
JP2017174648A (ja) * 2016-03-24 2017-09-28 株式会社豊田中央研究所 蓄電デバイス
CN106654165A (zh) * 2016-11-08 2017-05-10 珠海光宇电池有限公司 一种锂离子电池极片、制备方法及锂离子电池
CN110010897A (zh) * 2019-04-16 2019-07-12 江苏碳谷二维世界科技有限公司 一种石墨烯锂电池正极浆料、制备方法及锂电池正极极片

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