WO2024087390A1 - 二次电池及用电装置 - Google Patents

二次电池及用电装置 Download PDF

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Publication number
WO2024087390A1
WO2024087390A1 PCT/CN2022/144293 CN2022144293W WO2024087390A1 WO 2024087390 A1 WO2024087390 A1 WO 2024087390A1 CN 2022144293 W CN2022144293 W CN 2022144293W WO 2024087390 A1 WO2024087390 A1 WO 2024087390A1
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Prior art keywords
secondary battery
positive electrode
negative electrode
value
active material
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PCT/CN2022/144293
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English (en)
French (fr)
Inventor
张耀
王明旺
张旭辉
王宝玉
陈辉
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欣旺达动力科技股份有限公司
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Publication of WO2024087390A1 publication Critical patent/WO2024087390A1/zh

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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
    • 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 belongs to the field of battery technology, and specifically relates to a secondary battery and an electrical device.
  • the present application provides a secondary battery and an electrical device, aiming to increase the cycle life of the secondary battery.
  • a secondary battery of the present application has a capacity of n 1 Ah at 1C, an internal resistance of R m ⁇ at 0% SOC, and n 1 and R satisfy: 30 ⁇ n 1 ⁇ R ⁇ 90, wherein 5 ⁇ n 1 ⁇ 500, and 0.05 ⁇ R ⁇ 18.
  • the secondary battery includes a positive electrode plate and a negative electrode plate
  • the positive electrode plate includes a positive electrode collector, a positive electrode active material layer disposed on the positive electrode collector, and a positive electrode tab extending from the positive electrode collector, and the positive electrode active material layer contains lithium iron phosphate
  • the negative electrode plate includes a negative electrode collector, a negative electrode active material layer disposed on the negative electrode collector, and a negative electrode tab extending from the negative electrode collector, and the negative electrode active material layer contains graphite.
  • the number of the positive electrode tabs is N c
  • the number of the negative electrode tabs is N a , satisfying: N a >N c , wherein 2 ⁇ N c ⁇ 100, 4 ⁇ N a ⁇ 102.
  • the number N c of the positive electrode tabs and the number N a of the negative electrode tabs further satisfy: N a -N c ⁇ 2.
  • the thickness of the positive electrode active material layer is H c ⁇ m
  • the thickness of the negative electrode active material layer is H a ⁇ m, satisfying: H a ⁇ H c , wherein 30 ⁇ H a ⁇ 250, 50 ⁇ H c ⁇ 400.
  • the thickness H c of the positive electrode active material layer and the thickness Ha of the negative electrode active material layer further satisfy: 1.0 ⁇ H c /H a ⁇ 2.0.
  • the design CB value of the secondary battery is 0.8 to 1.1;
  • the designed CB value is the capacity ratio of the negative electrode sheet capacity per unit area to the positive electrode sheet capacity per unit area.
  • n 1 , R, and the designed CB value satisfy: 25 ⁇ n 1 ⁇ R/CB ⁇ 100.
  • the actual usage CB’ value of the secondary battery is 1.1 ⁇ 1.3.
  • an electrical device of the present application includes the above-mentioned secondary battery, and the secondary battery serves as a power supply for the electrical device.
  • the present application provides a secondary battery with a specific capacity and a specific internal resistance by limiting the capacity and internal resistance of the secondary battery to satisfy: 30 ⁇ n 1 ⁇ R ⁇ 90, so as to increase the reversible capacity of the positive electrode sheet of the secondary battery, and balance the insertion and extraction rates of lithium ions of the positive and negative electrode materials to maintain the balance of electrochemical reactions of the secondary battery during operation, thereby improving the energy efficiency of the secondary battery and ultimately improving the cycle life and storage life of the secondary battery.
  • the present application provides a secondary battery and an electrical device. To make the purpose, technical solution and effect of the present application clearer and more specific, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present application and are not used to limit the present application.
  • Secondary batteries such as those in electric vehicles, need to extend their single-time driving range and service life as much as possible.
  • the loss of active lithium in the secondary batteries in electric vehicles during the charging and discharging process is the main factor in the attenuation of the secondary battery life.
  • the SEI film is broken and generated, the area and thickness of the SEI film increase, and the limited active lithium in the battery system is consumed, which ultimately shortens the battery life.
  • secondary batteries are all "replenished with lithium" through the negative electrode.
  • the rate of lithium deintercalation of the positive and negative electrodes in the secondary battery also has a certain impact on the life of the secondary battery.
  • the rate of lithium deintercalation of the positive and negative electrodes does not match, the secondary battery will experience lithium precipitation or capacity decay during operation, and its life and energy efficiency will decrease.
  • the internal resistance of the secondary battery also has an impact on the life of the secondary battery.
  • the internal resistance of the secondary battery is large, the heat loss itself is large during the charging and discharging process, the temperature is high during use, and the performance of the secondary battery is deteriorated.
  • the present application provides a secondary battery with a specific capacity and a specific internal resistance to increase the reversible capacity of the positive electrode plate of the secondary battery, while balancing the insertion and extraction rates of lithium ions of the positive and negative electrode materials to maintain the balance of the electrochemical reactions of the secondary battery during operation, thereby improving the energy efficiency of the secondary battery and ultimately improving the cycle life and storage life of the secondary battery.
  • the present application provides a secondary battery, which includes a positive electrode plate, a separator, an electrolyte and a negative electrode plate as described below.
  • a feature of the secondary battery of the present application is that the capacity of the secondary battery under 1C conditions is n 1 Ah, the internal resistance of the secondary battery under 0% SOC conditions is R m ⁇ , and n 1 and R satisfy: 30 ⁇ n 1 ⁇ R ⁇ 90, wherein the capacity n 1 represents the discharge capacity. That is, the product value of the capacity n 1 and the internal resistance R of the secondary battery can be controlled within the range of 30 to 90.
  • the product value of the capacity n 1 and the internal resistance R of the secondary battery can be 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or a range consisting of any two of them. It is worth noting that the specific numerical value of the product value is only given by way of example, and any value of the product value within the range of 30 to 90 is within the protection scope of the present application.
  • the internal resistance of a secondary battery has a certain relationship with the life of the secondary battery.
  • the internal resistance of a secondary battery is large, the heat loss of the secondary battery itself during the charge and discharge process is large, and the temperature of the secondary battery rises during use to further deteriorate the battery performance.
  • the internal resistance of the secondary battery is simply reduced, the system stability of the secondary battery will deteriorate, and the entire cycle life will also deteriorate.
  • the relationship between the capacity n1 of the secondary battery under 1C conditions and the internal resistance R of the secondary battery under 0% SOC conditions is limited to meet the above range, so as to optimize the relationship between the capacity n1 and the internal resistance R, balance the deintercalation rate of lithium ions of the positive and negative electrode materials, maintain the balance of electrochemical reactions of the secondary battery during operation, improve the energy efficiency of the secondary battery, and ultimately improve the cycle life and storage life of the secondary battery.
  • the capacity n 1 Ah of the above-mentioned secondary battery under 1C conditions satisfies: 5 ⁇ n 1 ⁇ 500. That is, the capacity n 1 Ah of the secondary battery under 1C conditions can be controlled within the range of 5Ah to 500Ah.
  • the capacity n 1 Ah of the secondary battery under 1C conditions can be one of 5Ah, 50Ah, 100Ah, 150Ah, 200Ah, 250 Ah, 300Ah, 350Ah, 400Ah, 450Ah, 500Ah, or a range consisting of any two of them.
  • the internal resistance R m ⁇ of the above-mentioned secondary battery under 0% SOC conditions satisfies: 0.05 ⁇ R ⁇ 18.
  • the internal resistance R m ⁇ of the secondary battery under 0% SOC conditions can be controlled within the range of 0.05m ⁇ to 18m ⁇ .
  • the internal resistance R m ⁇ of the secondary battery under 0% SOC conditions can be 0.05m ⁇ , 0.5m ⁇ , 1m ⁇ , 2m ⁇ , 3m ⁇ h, 4m ⁇ , 5m ⁇ , 6m ⁇ , 7m ⁇ , 8m ⁇ , 9m ⁇ , 10m ⁇ , 11m ⁇ , 12m ⁇ , 13m ⁇ h, 14m ⁇ , 15m ⁇ , 16m ⁇ , 17m ⁇ , 18m ⁇ , or a range consisting of any two of them.
  • the specific value of the internal resistance R m ⁇ is only given as an example, and any value of the internal resistance R m ⁇ within the range of 0.05m ⁇ to 18m ⁇ is within the protection scope of this application.
  • the capacity n 1 of the secondary battery under 1C conditions is controlled within the above range
  • the internal resistance R of the secondary battery under 0% SOC conditions is controlled within the above range, so that the relationship between the capacity n 1 of the secondary battery under 1C conditions and the internal resistance R of the secondary battery under 0% SOC conditions satisfies: 30 ⁇ n 1 ⁇ R ⁇ 90, so as to optimize the relationship between the capacity n 1 and the internal resistance R, balance the insertion and extraction rates of lithium ions of the positive and negative electrode materials, maintain the balance of electrochemical reactions of the secondary battery during operation, improve the energy efficiency of the secondary battery, and ultimately improve the cycle life and storage life of the secondary battery.
  • the positive electrode plate includes, but is not limited to, a positive electrode active material layer, the positive electrode active material layer can be provided with one or more layers, and each layer of the multi-layer positive electrode active material can contain the same or different positive electrode active materials.
  • the positive electrode active material is any substance that can reversibly embed and de-embed metal ions such as lithium ions.
  • the positive electrode active material layer includes, but is not limited to, positive electrode active materials, including, but not limited to, lithium iron phosphate, lithium iron manganese phosphate, lithium manganate and ternary materials.
  • positive electrode active materials can be used alone or in any combination.
  • the ternary material includes, but is not limited to, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminum oxide.
  • the positive electrode active material may further include doping elements, and the doping elements may include one or more elements of aluminum, magnesium, titanium, zirconium, vanadium, and tungsten, as long as the structure of the positive electrode active material can be made more stable.
  • the positive electrode active material may further include a coating element, and the coating element may include one or more elements selected from aluminum, magnesium, titanium, zirconium, fluorine, and boron, as long as the structure of the positive electrode active material can be made more stable.
  • the positive electrode plate includes, but is not limited to, a positive electrode conductive agent.
  • the type of the positive electrode conductive agent in the present application is not limited, and any known conductive material can be used as long as it does not damage the effect of the present application.
  • the positive electrode conductive agent may include, but is not limited to, natural graphite, artificial graphite, acetylene black, carbon black, needle coke, amorphous carbon, carbon nanotubes, and graphene.
  • the above positive electrode conductive materials can be used alone or in any combination.
  • the positive electrode sheet includes, but is not limited to, a positive electrode binder.
  • the type of positive electrode binder used in the manufacture of the positive electrode active material layer is not particularly limited as long as it does not impair the effect of the present application. Specifically, it can be any material that is soluble or dispersible in the liquid medium used in the manufacture of the electrode.
  • the positive electrode plate includes, but is not limited to, a positive electrode current collector, the positive electrode active material layer is disposed on the positive electrode current collector, and the type of the positive electrode current collector is not particularly limited, and it can be any material known to be suitable for use as a positive electrode current collector, as long as it does not impair the effect of the present application.
  • the positive electrode current collector may include, but is not limited to, metal materials such as aluminum, stainless steel, nickel plating, titanium, tantalum, and carbon materials such as carbon cloth and carbon paper.
  • the positive electrode current collector is a metal material.
  • the positive electrode current collector is aluminum foil.
  • a positive electrode tab extends from the positive electrode current collector.
  • the positive electrode tab can be obtained by cutting the positive electrode current collector.
  • the positive electrode sheet in the secondary battery of the present application can be prepared by any known method.
  • a conductive agent, a binder, and a solvent are added to the positive electrode active material to form a slurry, and the slurry is coated on the positive electrode collector, and the electrode is formed by pressing after drying.
  • the positive electrode active material can also be roll-formed into a sheet electrode, or compressed into a granular electrode.
  • the negative electrode plate includes, but is not limited to, a negative electrode active material layer, the negative electrode active material layer may be one or more layers, and each layer of the multiple layers of negative electrode active materials may contain the same or different negative electrode active materials.
  • the chargeable capacity of the negative electrode active material is greater than the discharge capacity of the positive electrode active material to prevent lithium metal from precipitating and growing on the negative electrode plate during charging.
  • the negative electrode active material layer includes, but is not limited to, a negative electrode active material, and the negative electrode active material includes, but is not limited to, graphite.
  • the negative electrode active material includes, but is not limited to, artificial graphite, natural graphite, soft carbon, hard carbon, amorphous carbon, carbon fiber carbon nanotubes and mesophase carbon microspheres.
  • artificial graphite, natural graphite, soft carbon, hard carbon, amorphous carbon, carbon fiber carbon nanotubes and mesophase carbon microspheres can be used alone or in any combination.
  • the negative electrode plate includes, but is not limited to, a negative electrode current collector, the negative electrode active material layer is disposed on the negative electrode current collector, and the type of the negative electrode current collector is not particularly limited, and it can be any material known to be suitable for use as a negative electrode current collector, as long as it does not impair the effect of the present application.
  • the negative electrode current collector includes, but is not limited to, metal foil, metal cylinder, metal strip roll, metal plate, metal film, metal plate mesh, stamped metal, foamed metal, etc.
  • the negative electrode current collector is a metal foil.
  • the negative electrode current collector is a copper foil.
  • the term "copper foil" includes copper alloy foil.
  • a negative electrode tab extends from the negative electrode current collector.
  • the negative electrode tab can be obtained by cutting the negative electrode current collector.
  • the negative electrode sheet in the secondary battery of the present application can be prepared by any known method.
  • a conductive agent, a binder, an additive and a solvent are added to the negative electrode active material to form a slurry, and the slurry is coated on the negative electrode collector, and the electrode is formed by pressing after drying.
  • the negative electrode active material can also be roll-formed into a sheet electrode, or compressed into a granular electrode.
  • the number of the positive electrode tabs is N c
  • the number of the negative electrode tabs is N a , satisfying: N a > N c ,
  • the number Nc of the positive electrode tabs satisfies: 2 ⁇ Nc ⁇ 100 . That is, the number Nc of the positive electrode tabs can be controlled within the range of 2 to 100.
  • the number Nc of the positive electrode tabs can be one of 2, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or a range consisting of any two of them. It is worth noting that the specific numerical value of the number Nc is only given as an example, and any value of the number Nc within the range of 2 to 100 is within the protection scope of this application.
  • the number Na of the negative electrode tabs satisfies: 4 ⁇ N a ⁇ 102. That is, the number Na of the negative electrode tabs can be controlled within the range of 4 to 102.
  • the number Na of the negative electrode tabs can be one of 4, 12, 22, 32, 42, 52, 62, 72, 82, 92, 102 or a range consisting of any two of them. It is worth noting that the specific value of the number Na is only given as an example, and any value of the number Na within the range of 4 to 102 is within the protection scope of the present application.
  • the number N c of the positive electrode tabs and the number N a of the negative electrode tabs further satisfy: N a -N c ⁇ 2.
  • the relationship between the number of positive electrode tabs Nc and the number of negative electrode tabs Na satisfies the above range to adjust the number of positive electrode tabs and negative electrode tabs, and control the number of negative electrode tabs to be greater than the number of positive electrode tabs, thereby improving the polarization of the positive electrode, enhancing the stability of the positive electrode active material, and thus improving the cycle performance of the secondary battery.
  • the thickness of the positive electrode active material layer is H c ⁇ m
  • the thickness of the negative electrode active material layer is H a ⁇ m, satisfying: H a ⁇ H c ,
  • the thickness Ha of the negative electrode active material layer satisfies: 30 ⁇ H a ⁇ 250. That is, the thickness Ha ⁇ m of the negative electrode active material layer can be controlled within the range of 30 ⁇ m to 250 ⁇ m.
  • the thickness Ha ⁇ m of the negative electrode active material layer can be 30 ⁇ m, 50 ⁇ m, 70 ⁇ m, 90 ⁇ m, 110 ⁇ m, 130 ⁇ m, 150 ⁇ m, 170 ⁇ m, 190 ⁇ m, 210 ⁇ m, 230 ⁇ m, 250 ⁇ m, or a range consisting of any two of them.
  • the specific value of the thickness Ha ⁇ m is only given as an example, and any value of the thickness Ha ⁇ m within the range of 30 ⁇ m to 250 ⁇ m is within the protection scope of this application.
  • H c and Ha refer to the total thickness of the active material layer, that is, the sum of the thicknesses of the active material layers located on both sides of the current collector.
  • the thickness H a of the negative electrode active material layer is controlled within the above range to optimize the thickness of the negative electrode active material layer, so as to balance the deintercalation rate of lithium ions of the positive and negative electrode materials, maintain the balance of the electrochemical reaction of the secondary battery during operation, and improve the cycle life and storage life of the secondary battery.
  • the thickness H c ⁇ m of the positive electrode active material layer satisfies: 50 ⁇ H c ⁇ 400. That is, the thickness H c ⁇ m of the positive electrode active material layer can be controlled within the range of 50 ⁇ m to 400 ⁇ m.
  • the thickness H c of the negative active material layer can be one of 50 ⁇ m, 100 ⁇ m, 150 ⁇ m, 200 ⁇ m, 250 ⁇ m, 300 ⁇ m, 350 ⁇ m, 400 ⁇ m or a range consisting of any two of them.
  • the specific value of the thickness H c is only given by way of example, as long as the thickness H c ⁇ m is any value within the range of 50 ⁇ m to 400 ⁇ m, it is within the protection scope of this application.
  • the thickness of the positive electrode active material layer is optimized to balance the deintercalation rate of lithium ions of the positive and negative electrode materials, so as to maintain the balance of electrochemical reactions of the secondary battery during operation, and to improve the cycle life and storage life of the secondary battery.
  • the thickness Hc of the positive electrode active material layer and the thickness Ha of the negative electrode active material layer also satisfy: 1.0 ⁇ Hc / Ha ⁇ 2.0 . That is, the ratio of the thickness Hc of the positive electrode active material layer to the thickness Ha of the negative electrode active material layer can be controlled within the range of 1.0 to 2.0.
  • the ratio of the thickness Hc of the positive electrode active material layer to the thickness Ha of the negative electrode active material layer can be one of 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0 or a range consisting of any two of them. It is worth noting that the specific numerical value of the ratio is only given as an example, and any value of the ratio within the range of 1.0 to 2.0 is within the protection scope of the present application.
  • the relationship between the thickness Hc of the positive electrode active material layer and the thickness Ha of the negative electrode active material layer is controlled within the above range to balance the deintercalation rate of lithium ions of the positive and negative electrode materials, so as to maintain the balance of the electrochemical reaction of the secondary battery during operation and improve the cycle life and storage life of the secondary battery.
  • the design CB value of the secondary battery is 0.8-1.1; that is, the design CB value of the secondary battery can be controlled within the range of 0.8-1.1.
  • the design CB value of the secondary battery can be one of 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1 or a range consisting of any two of them.
  • the designed CB value is the capacity ratio of the negative electrode sheet capacity per unit area to the positive electrode sheet capacity per unit area.
  • the unit area of the positive and negative electrode sheets must be kept equal when calculating the design CB value.
  • the secondary battery is charged in a constant capacity manner during operation so that the positive electrode plate releases only a portion of lithium ions, and the excess lithium ions are used as a reserve to supplement the loss of active lithium in the secondary battery during operation.
  • the design CB value of the secondary battery is controlled within the above-mentioned range, so as to design the positive electrode plate of the secondary battery with surplus lithium ions, so that a large amount of spare active lithium is stored in the positive electrode plate of the secondary battery, and the reversible capacity of the positive electrode plate of the secondary battery is increased to supplement the loss of active lithium during the cycle and storage of the secondary battery, maintain the balance of electrochemical reactions during the working process of the entire secondary battery system, so as to improve the cycle life and storage life of the secondary battery; at the same time, in the present application, the positive electrode plate of the secondary battery is designed with surplus lithium ions, so that the depth of lithium desorption of the secondary battery during the cycle process is low, and the polarization and resistance of the secondary battery are small, thereby improving the energy efficiency of the secondary battery.
  • test method of the designed CB value of the secondary battery is:
  • step S3 Based on the negative electrode sheet capacity per unit area and the positive electrode sheet capacity per unit area obtained in step S1 and step S2, the ratio of the two is calculated to obtain the designed CB value.
  • the capacity n 1 of the secondary battery under 1C condition, the internal resistance R of the secondary battery under 0% SOC condition, and the designed CB value satisfy: 25 ⁇ n 1 ⁇ R/CB ⁇ 100.
  • n 1 , R and the designed CB value to satisfy 25 ⁇ n 1 ⁇ R/CB ⁇ 100
  • the relationship between the capacity n 1 of the secondary battery under 1C conditions, the internal resistance R of the secondary battery under 0% SOC conditions and the designed CB value is optimized, so as to balance the lithium ion insertion and extraction rates of the positive and negative electrode active materials in the positive and negative electrode sheets, so as to maintain the balance of the electrochemical reactions in the working process of the entire secondary battery system, thereby improving the energy efficiency of the secondary battery, and ultimately improving the cycle life and storage life of the secondary battery.
  • the actual use CB' value of the secondary battery is 1.1 ⁇ 1.3. That is, the actual use CB' value of the secondary battery can be controlled within the range of 1.1 ⁇ 1.3.
  • the actual use CB' value of the secondary battery can be one of 1.1, 1.12, 1.14, 1.16, 1.18, 1.2, 1.22, 1.24, 1.26, 1.28, 1.3 or a range consisting of any two of them. It is worth noting that the specific numerical value of the actual use CB' value is only given as an example, as long as the actual use CB' value is any value within the range of 1.1 ⁇ 1.3, it is within the protection scope of the present application.
  • the actual use CB' value of the secondary battery is controlled within the above range so that the secondary battery will not produce lithium plating during actual use, thereby reducing or even avoiding the consumption of active lithium during actual use of the secondary battery and improving the life of the secondary battery.
  • the electrolyte used in the secondary battery of the present application includes an electrolyte and a solvent that dissolves the electrolyte.
  • the electrolyte in the present application, and any known substance as an electrolyte can be used as long as the effect of the present application is not impaired.
  • a lithium salt is generally used.
  • the electrolyte includes, but is not limited to, LiPF 6 .
  • the electrolyte content in the present application can be 0.8 mol/L to 2.2 mol/L.
  • the solvent includes, but is not limited to, ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), butylene carbonate (BC) and methyl ethylene carbonate (MEC).
  • EC ethylene carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • BC butylene carbonate
  • MEC methyl ethylene carbonate
  • a separator is usually provided between the positive electrode and the negative electrode to prevent short circuit.
  • the electrolyte of the present application is usually used by infiltrating the separator.
  • the present application further provides an electric device, comprising a secondary battery as described in any one of the above items, wherein the secondary battery serves as a power supply for the electric device.
  • the electrical devices include electric vehicles, energy storage batteries, etc.
  • lithium-ion batteries The preparation of lithium-ion batteries is described below by taking lithium-ion batteries as an example and combining specific embodiments. Those skilled in the art will understand that the preparation method described in this application is only an embodiment, and any other suitable preparation method is within the scope of this application.
  • the positive electrode active material lithium iron phosphate, the conductive agent conductive carbon black SP, and the binder PVDF are mixed in a mass ratio of 97:0.7:2.3, and then NMP is added as a solvent for mixing. After stirring for a certain period of time, a uniform positive electrode slurry with a certain fluidity is obtained; the positive electrode slurry is evenly coated on both sides of the positive electrode current collector carbon-coated aluminum foil, and then transferred to a 120°C oven for drying, and then rolled, slit, and cut into pieces to obtain the positive electrode sheet.
  • the negative electrode active material graphite, the conductive agent conductive carbon black SP, the thickener CMC, and the binder SBR are mixed in a mass ratio of 96.5:0.5:1.2:1.8, and then deionized water is added as a solvent for mixing. After stirring for a certain period of time, a uniform negative electrode slurry with a certain fluidity is obtained; the negative electrode slurry is evenly coated on both sides of the negative electrode collector copper foil, and then transferred to a 110°C oven for drying, and then rolled, slit, and cut to obtain a negative electrode sheet.
  • Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were mixed in a volume ratio of 1:1:1, and then 1 mol/L LiPF 6 was added and mixed evenly to prepare an electrolyte.
  • PP film is used as the isolation film.
  • the negative electrode sheet and the positive electrode sheet prepared by the above steps are dried and then used together with the isolation film to prepare a wound battery cell using a winding machine.
  • the positive electrode tab and the negative electrode tab are welded to the top cover of the battery cell, and the welded battery cell with the top cover is placed in an aluminum shell for packaging; the lithium-ion battery is obtained by filling the electrolyte and forming a constant capacity.
  • the capacity n 1 Ah of the lithium ion battery under 1C condition is 5 Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 18 m ⁇
  • the number N c of the positive electrode tabs is 2
  • the number N a of the negative electrode tabs is 4
  • the thickness H c ⁇ m of the positive electrode active material layer is 50 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 30 ⁇ m
  • the designed CB value of the secondary battery is 1.1
  • n 1 , R and the designed CB value satisfy: 81.8
  • the actual use CB' value of the secondary battery is
  • the prepared lithium ion battery was charged at a constant capacity of 1C to the nominal capacity, and discharged at a 1C rate to 2.5V, and a cycle test was performed until the capacity of the lithium ion secondary battery decayed to 80% of the initial capacity, and the number of cycles was recorded.
  • the prepared lithium-ion battery was charged to the nominal capacity at a 1C rate and discharged to 2.5V at a 1C rate to obtain the initial capacity of the battery. After the battery was fully charged at a 1C rate, the battery was placed in a constant temperature box at 60°C until the capacity of the lithium-ion secondary battery decayed to 80% of the initial capacity, and the number of days of storage was recorded.
  • the prepared lithium-ion battery was charged at a constant current of 1C to the nominal capacity of the battery, recorded as the charging energy E 1 , left to stand for 30 min, and then discharged at a constant current of 1C to the voltage lower limit (2.5 V), recorded as the discharge energy E 2 , and the energy efficiency value E 2 / E 1 of the lithium-ion battery was calculated.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 50Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 0.6 m ⁇
  • the design CB value of the secondary battery is 1.07
  • the actual use CB' value of the secondary battery is 1.12.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 100Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 0.37 m ⁇
  • the design CB value of the secondary battery is 1.04
  • the actual use CB' value of the secondary battery is 1.14.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium-ion battery under 1C condition is 150Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 0.31 m ⁇
  • the design CB value of the secondary battery is 1.01
  • the actual use CB' value of the secondary battery is 1.16.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 200Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 0.28m ⁇
  • the design CB value of the secondary battery is 0.98
  • the actual use CB' value of the secondary battery is 1.18.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 250Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 0.2 m ⁇
  • the design CB value of the secondary battery is 0.95
  • the actual use CB' value of the secondary battery is 1.2.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 300Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 0.18m ⁇
  • the designed CB value of the secondary battery is 0.92
  • the actual used CB' value of the secondary battery is 1.22.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method of Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 350Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 0.16m ⁇
  • the design CB value of the secondary battery is 0.89
  • the actual use CB' value of the secondary battery is 1.24.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 400Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 0.15 m ⁇
  • the design CB value of the secondary battery is 0.86
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 450Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 0.13 m ⁇
  • the design CB value of the secondary battery is 0.83
  • the actual use CB' value of the secondary battery is 1.28.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 500Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 0.12 m ⁇
  • the design CB value of the secondary battery is 0.8
  • the actual use CB' value of the secondary battery is 1.3.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 30 Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 1 m ⁇
  • the design CB value of the secondary battery is 1.08
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 15 Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 5 m ⁇
  • the design CB value of the secondary battery is 1.085
  • the actual use CB' value of the secondary battery is 1.112.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 8Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 10m ⁇
  • the design CB value of the secondary battery is 1.09
  • the actual use CB' value of the secondary battery is 1.108.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 6Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 15m ⁇
  • the design CB value of the secondary battery is 1.095
  • the actual use CB' value of the secondary battery is 1.104.
  • the capacity n 1 of the lithium ion battery can be controlled by adjusting the content of the positive active material lithium iron phosphate, and the internal resistance R of the lithium ion battery can be controlled by controlling the capacity and adjusting the content of the conductive carbon black in the positive and/or negative electrode sheets to obtain the lithium ion batteries corresponding to Examples 1-15.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method of Example 1, except for the following differences:
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method of Example 1, except for the following differences:
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method of Example 1, except for the following differences:
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method of Example 1, except for the following differences:
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method of Example 1, except for the following differences:
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • Examples 16 to 27 corresponding lithium-ion batteries can be obtained by adjusting the number of welds between the positive electrode tab and the negative electrode tab.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method of Example 1, except for the following differences:
  • the thickness H c ⁇ m of the positive electrode active material layer is 70 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 50 ⁇ m
  • the designed CB value of the secondary battery is 1.085
  • the actual use CB' value of the secondary battery is 1.105.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method of Example 1, except for the following differences:
  • the thickness H c ⁇ m of the positive electrode active material layer is 80 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 80 ⁇ m
  • the designed CB value of the secondary battery is 1.055
  • the actual use CB' value of the secondary battery is 1.125.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • the thickness H c ⁇ m of the positive electrode active material layer is 120 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 100 ⁇ m
  • the designed CB value of the secondary battery is 1.025
  • the actual use CB' value of the secondary battery is 1.145.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method of Example 1, except for the following differences:
  • the thickness H c ⁇ m of the positive electrode active material layer is 150 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 120 ⁇ m
  • the designed CB value of the secondary battery is 0.995
  • the actual use CB' value of the secondary battery is 1.165.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • the thickness H c ⁇ m of the positive electrode active material layer is 190 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 140 ⁇ m
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method of Example 1, except for the following differences:
  • the thickness H c ⁇ m of the positive electrode active material layer is 235 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 160 ⁇ m
  • the designed CB value of the secondary battery is 0.935
  • the actual use CB' value of the secondary battery is 1.205.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method of Example 1, except for the following differences:
  • the thickness H c ⁇ m of the positive electrode active material layer is 360 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 180 ⁇ m
  • the designed CB value of the secondary battery is 0.905
  • the actual use CB' value of the secondary battery is 1.225.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • the thickness H c ⁇ m of the positive electrode active material layer is 350 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 200 ⁇ m
  • the designed CB value of the secondary battery is 0.875
  • the actual use CB' value of the secondary battery is 1.245.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • the thickness H c ⁇ m of the positive electrode active material layer is 370 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 230 ⁇ m
  • the designed CB value of the secondary battery is 0.845
  • the actual use CB' value of the secondary battery is 1.265.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method of Example 1, except for the following differences:
  • the thickness H c ⁇ m of the positive electrode active material layer is 400 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 250 ⁇ m
  • the designed CB value of the secondary battery is 0.8
  • the actual use CB' value of the secondary battery is 1.30.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • the thickness H c ⁇ m of the positive electrode active material layer is 70 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 30 ⁇ m
  • the designed CB value of the secondary battery is 1.16
  • the actual use CB' value of the secondary battery is 1.08.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • the thickness H c ⁇ m of the positive electrode active material layer is 240 ⁇ m
  • the thickness H a ⁇ m of the negative electrode active material layer is 260 ⁇ m
  • the designed CB value of the secondary battery is 0.77
  • the actual use CB' value of the secondary battery is 1.32.
  • Examples 28 to 39 corresponding lithium-ion batteries can be obtained by adjusting the coating thickness of the positive electrode active material layer and the negative electrode active material layer.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 4Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 28 m ⁇
  • the design CB value of the secondary battery is 1.12
  • the actual use CB' value of the secondary battery is 1.08.
  • a lithium ion battery was prepared according to the method of Example 1, and the lithium ion battery was tested according to the test method in Example 1, except for the following differences:
  • n 1 Ah of the lithium ion battery under 1C condition is 60Ah
  • the internal resistance R m ⁇ under 0% SOC condition is 0.03 m ⁇
  • the design CB value of the secondary battery is 0.79
  • the actual use CB' value of the secondary battery is 1.31.
  • Example 1 The n1 R n1 ⁇ R Design CB value n1 ⁇ R/CB Actual use of CB' value Energy efficiency at 25°C 25°C Cycle life (cycles) 60°C Storage life (days)
  • Example 1 5 18 90 1.1 81.8 1.1 93.20% 4117 430
  • Example 2 50 0.6 30 1.07 28.0 1.12 93.29% 4532 515
  • Example 3 100 0.37 37 1.04 35.6 1.14 93.32% 4987 575
  • Example 4 150 0.31 46.5 1.01 46.0 1.16 93.35% 5515 635
  • Example 5 200 0.28 56 0.98 57.1 1.18 93.42% 5951 695
  • Example 6 250 0.2 50 0.95 52.6 1.2 93.61% 6322 740
  • Example 7 300 0.18 54 0.92 58.7 1.22 94.03% 6768 785
  • Example 8 350 0.16 56 0.89 62.9 1.24 94.17% 7015 815
  • Example 9 400 0.15 60 0.86 69.8 1.26 94.39% 7418 845
  • This application adopts a lower design CB value and a normal use CB value to make the active lithium of the positive electrode abundant, so as to supplement the active lithium loss of the secondary battery during operation; and by limiting the capacity of the secondary battery, the internal resistance of the secondary battery, and the relationship between the capacity of the secondary battery, the internal resistance and the design CB value, the lithium ion deintercalation rate of the positive and negative pole pieces is balanced, so that the electrochemical reaction balance during the operation of the entire secondary battery system is optimal, thereby improving the energy efficiency and life of the secondary battery.
  • this application has significantly improved the cycle life at 25°C, the storage life at 60°C and the energy efficiency at 25°C.
  • the present invention adopts a lower design CB value and a normal use CB value to make the active lithium of the positive electrode abundant, so as to supplement the active lithium loss of the secondary battery during operation; and by limiting the number of positive and negative pole tabs of the secondary battery and the difference in the number of positive and negative pole tabs, the lithium ion deintercalation rate of the positive and negative pole pieces is balanced, so that the electrochemical reaction balance during the operation of the entire secondary battery system reaches a better state, thereby improving the energy efficiency and life of the secondary battery.
  • the present application has significantly improved the cycle life at 25°C, the storage life at 60°C and the energy efficiency at 25°C.
  • This application adopts a lower design CB value and a normal actual use CB' value to make the active lithium of the positive electrode abundant, so as to supplement the active lithium loss of the secondary battery during operation; and by limiting the thickness of the positive and negative electrode sheets of the secondary battery and the ratio of the thickness of the positive and negative electrode sheets, the lithium ion deintercalation rate of the positive and negative electrode sheets is balanced, so that the electrochemical reaction balance during the operation of the entire secondary battery system is optimal, thereby improving the energy efficiency and life of the secondary battery.
  • this application has significantly improved the cycle life at 25°C, the storage life at 60°C, and the energy efficiency at 25°C.

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Abstract

公开一种二次电池及用电装置，二次电池在1C条件下的容量为n1 Ah，所述二次电池在0%SOC条件下的内阻为R mΩ，n1和R之间满足：30≤n1×R≤90，其中5≤n1≤500，0.05≤R≤18。本申请通过限定二次电池的容量与内阻满足：30≤n1×R≤90，以提供了具有特定容量及特定内阻的二次电池，以增加二次电池的正极极片的可逆容量，同时平衡正负极材料锂离子的脱嵌速率，以维持二次电池在工作过程中电化学反应的平衡，提升了二次电池的能量效率，最终提升二次电池的循环寿命及存储寿命。

Description

二次电池及用电装置
本申请要求于2022年10月27日提交中国专利局、申请号为202211327803.9、发明名称为“二次电池及用电装置”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，具体涉及一种二次电池及用电装置。
 背景技术
随着新能源行业的快速发展，对于有更大容量、更耐用二次电池、具有更为长久续航能力的能量型二次电池的需求十分迫切。活性锂材料作为二次电池的核心部分之一，其在电池循环过程中会不断被消耗而出现衰减，从而导致电池容量以及循环寿命的不断降低。因此，减少或补充在电池循环过程中的活性锂消耗，是提升二次电池的循环寿命的有效途径之一。因此，如何减少或补充在电池衰减过中的活性锂消耗，以提高二次电池的循环寿命成为亟待解决的问题。
 技术问题
本申请提供一种二次电池及用电装置，旨在提高二次电池的循环寿命。
 技术解决方案
第一方面，本申请的一种二次电池，所述二次电池在1C条件下的容量为n 1 Ah，所述二次电池在0%SOC条件下的内阻为R mΩ，n 1和R之间满足：30≤n 1×R≤90，其中5≤n 1≤500，0.05≤R≤18。
在一些实施例中，所述二次电池包括正极极片和负极极片，所述正极极片包括正极集流体、设置于所述正极集流体上的正极活性材料层、以及从所述正极集流体上延伸出的正极极耳，所述正极活性材料层包含磷酸铁锂；所述负极极片包括负极集流体、设置于所述负极集流体上的负极活性材料层、以及从所述负极集流体上延伸出的负极极耳，所述负极活性材料层包含石墨。
在一些实施例中，所述正极极耳的数量为N c个，所述负极极耳的数量为N a个，满足：N a >N c，其中2≤N c≤100，4≤N a≤102。
在一些实施例中，所述正极极耳的数量N c与所述负极极耳的数量N a还满足：N a-N c≥2。
在一些实施例中，所述正极活性材料层的厚度为H cμm，所述负极活性材料层的厚度为H aμm，满足：H a≤H c，其中，30≤H a≤250，50≤H c≤400。
在一些实施例中，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a还满足：1.0≤H c/H a≤2.0。
在一些实施例中，所述二次电池的设计CB值为0.8~1.1；
其中，设计CB值为单位面积负极极片容量与单位面积正极极片容量的容量比。
在一些实施例中，n 1、R以及设计CB值之间满足：25≤n 1×R/CB≤100。
在一些实施例中，所述二次电池的实际使用CB’值为1.1~1.3。
第二方面，本申请的一种用电装置，包括上述的二次电池，所述二次电池作为所述用电装置的供电电源。
 有益效果
相较于现有技术，本申请通过限定二次电池的容量与内阻满足：30≤n 1×R≤90，以提供了具有特定容量及特定内阻的二次电池，以增加二次电池的正极极片的可逆容量，同时平衡正负极材料锂离子的脱嵌速率，以维持二次电池在工作过程中电化学反应的平衡，提升了二次电池的能量效率，最终提升二次电池的循环寿命及存储寿命。
本发明的实施方式
本申请提供一种二次电池及用电装置，为使本申请的目的、技术方案及效果更加清楚、明确，以下结合实施例对本申请进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。
随着新能源行业的发展，人们对二次电池提出了更高需求，二次电池，例如电动汽车中的二次电池，需要尽可能的延长其单次续航里程和使用寿命，电动汽车中的二次电池在充放电过程中活性锂的损失是二次电池寿命衰减的主要因素。二次电池循环脱嵌锂过程中，由于石墨的膨胀收缩、正极过渡金属溶出等原因，造成SEI膜的破裂和生成，SEI膜面积和厚度增加，消耗电池体系有限的活性锂，最终导致电池使用寿命缩短。目前，二次电池均是通过负极进行“补锂”。与此同时，二次电池中正负极的脱嵌锂速率对二次电池的寿命也具有一定的影响，当正负极脱嵌锂速率不匹配时，二次电池在工作过程中就会出现析锂或者容量衰减，其寿命和能量效率就会下降。同时，二次电池的内阻对二次电池的寿命也具有影响，当二次电池的内阻大时，充放电过程中自身热损耗大，使用中温度大，恶化二次电池性能。
为了改善上述问题，本申请提供了具有特定容量及特定内阻的二次电池，以增加二次电池的正极极片的可逆容量，同时平衡正负极材料锂离子的脱嵌速率，以维持二次电池在工作过程中电化学反应的平衡，提升了二次电池的能量效率，最终提升二次电池的循环寿命及存储寿命。
在本申请的实施例中，本申请提供了一种二次电池，其包括如下所述的正极极片、隔离膜、电解液及负极极片。
在本申请的实施例中，本申请的二次电池的一个特征在于所述二次电池在1C条件下的容量为n 1 Ah，所述二次电池在0%SOC条件下的内阻为R mΩ，n 1和R之间满足：30≤n 1×R≤90，其中所述容量n 1表示放电容量。即二次电池的容量n 1和内阻R的乘积值可以控制在30～90范围内。比如，二次电池的容量n 1和内阻R的乘积值可以为30、35、40、45、50、55、60、65、70、75、80、85、90中的一者或其中任意二者组成的范围。值得说明的是，该乘积值的具体数值仅是示例性地给出，只要乘积值在30～90范围内的任意值均在本申请的保护范围内。
可以理解的，二次电池的内阻与二次电池的寿命具有一定关系，当二次电池的内阻大时，二次电池在充放电过程中自身热损耗就大，使用中二次电池的温度上升以更加恶化电池性能。同时，如果只单纯的降低二次电池的内阻，二次电池的体系稳定性变差，整个循环寿命也会变差。
本申请中通过限定二次电池在1C条件下的容量n 1与二次电池在0%SOC条件下的内阻R之间的关系满足上述范围，以对容量n 1与内阻R之间的关系进行优化，以平衡正负极材料锂离子的脱嵌速率，以维持二次电池在工作过程中电化学反应的平衡，提升了二次电池的能量效率，最终提升二次电池的循环寿命及存储寿命。
其中，上述的二次电池在1C条件下的容量n 1 Ah满足：5≤n 1≤500。即二次电池在1C条件下的容量n 1 Ah可以控制在5Ah～500Ah范围内。比如，二次电池在1C条件下的容量n 1 Ah可以为5Ah、50Ah、100Ah、150Ah、200Ah、250 Ah、300Ah、350Ah、400Ah、450Ah、500Ah中的一者或其中任意二者组成的范围。值得说明的是，该容量n 1 Ah的具体数值仅是示例性地给出，只要容量n 1 Ah在5Ah～500Ah范围内的任意值均在本申请的保护范围内。本申请中通过将二次电池在1C条件下的容量n 1 Ah控制在上述范围，
其中，上述的二次电池在0%SOC条件下的内阻R mΩ满足：0.05≤R≤18。二次电池在0%SOC条件下的内阻R mΩ可以控制在0.05mΩ～18mΩ范围内。比如，二次电池在0%SOC条件下的内阻R mΩ可以为0.05mΩ、0.5mΩ、1mΩ、2mΩ、3mΩh、4mΩ、5mΩ、6mΩ、7mΩ、8mΩ、9mΩ、10mΩ、11mΩ、12mΩ、13mΩh、14mΩ、15mΩ、16mΩ、17mΩ、18mΩ中的一者或其中任意二者组成的范围。值得说明的是，该内阻R mΩ的具体数值仅是示例性地给出，只要内阻R mΩ在0.05mΩ～18mΩ范围内的任意值均在本申请的保护范围内。
可以理解的，本申请中通过将二次电池在1C条件下的容量n 1控制在上述范围，同时将二次电池在0%SOC条件下的内阻R控制在上述范围，以使得二次电池在1C条件下的容量n 1与二次电池在0%SOC条件下的内阻R之间的关系满足：30≤n 1×R ≤90，以对容量n 1与内阻R之间的关系进行优化，以平衡正负极材料锂离子的脱嵌速率，以维持二次电池在工作过程中电化学反应的平衡，提升了二次电池的能量效率，最终提升二次电池的循环寿命及存储寿命。
在本申请的实施例中，所述正极极片包括，但不限于，正极活性材料层，所述正极活性材料层可以设置一层或多层，多层正极活性材料中的每层可以包含相同或不同的正极活性材料。正极活性材料为任何能够可逆地嵌入和脱嵌锂离子等金属离子的物质。
所述正极活性材料层包含，但不仅限于，正极活性材料，所述正极活性材料包括，但不限于，磷酸铁锂、磷酸锰铁锂、锰酸锂和三元材料。上述正极活性材料可单独使用或任意组合使用。
在本申请的实施例中，所述三元材料包括，但不仅限于，镍钴锰酸锂、镍钴铝酸锂。
在本申请的实施例中，所述正极活性材料还可包含掺杂元素，所述掺杂元素可以包含铝、镁、钛、锆、钒、钨中的一种或者多种元素，只要能使正极活性材料结构更稳定即可。
在本申请的实施例中，所述正极活性材料还可包含包覆元素，所述包覆元素可以包含铝、镁、钛、锆、氟、硼中的一种或者多种元素，只要能使正极活性材料结构更稳定即可。
在本申请的实施例中，所述正极极片包括，但不限于，正极导电剂，本申请中的正极导电剂中的种类没有限制，可以使用任何已知的导电材料，只要不损害本申请的效果即可。例如：正极导电剂可包括，但不限于，天然石墨、人造石墨、乙炔黑、炭黑、针状焦、无定形碳、碳纳米管、石墨烯。上述正极导电材料可单独使用或任意组合使用。
在本申请的实施例中，所述正极极片包括，但不限于，正极粘结剂，正极活性物质层的制造中使用的正极粘结剂的种类没有特别限制，只要不损害本申请的效果即可。具体的，只要是在电极制造时使用的液体介质中可溶解或分散的材料即可。
在本申请的实施例中，所述正极极片包括，但不限于，正极集流体，所述正极活性材料层设置于所述正极集流体上，正极集流体的种类没有特别限制，其可为任何已知适于用作正极集流体的材质，只要不损害本申请的效果即可。例如，所述正极集流体可包括，但不仅限于，铝、不锈钢、镍镀层、钛、钽等金属材料；碳布、碳纸等碳材料。在一实施例中，正极集流体为金属材料。在一实施例中，正极集流体为铝箔。
在本申请的实施例中，正极集流体上延伸出正极极耳。
在本申请的实施例中，可以通过裁切正极集流体的方式得到正极极耳。
在本申请的实施例中，本申请的二次电池中的正极极片可使用任何已知方法制备。例如，在正极活性材料中添加导电剂、粘结剂与溶剂等，制成浆料，将该浆料涂布在正极集流体上，干燥后通过压制而形成电极。也可以将正极活性物质进行辊成型制成片状电极，或通过压缩成型制成颗粒电极。
在本申请的实施例中，所述负极极片包括，但不限于，负极活性材料层，负极活性材料层可以是一层或多层，多层负极活性材料中的每层可以包含相同或不同的负极活性材料。在本申请的实施例中，负极活性材料的可充电容量大于正极活性材料的放电容量，以防止在充电期间锂金属析出并生长在负极极片上。
所述负极活性材料层包含，但不限于，负极活性材料，所述负极活性材料包含，但不限于，石墨。
在本申请的实施例中，所述负极活性材料包含，但不限于，人造石墨、天然石墨、软炭、硬炭、无定型碳、碳纤维碳纳米管和中间相炭微球。上述负极活性材料可单独使用或任意组合使用。
在本申请的实施例中，所述负极极片包括，但不限于，负极集流体，所述负极活性材料层设置于所述负极集流体上，负极集流体的种类没有特别限制，其可为任何已知适于用作负极集流体的材质，只要不损害本申请的效果即可。例如，所述负极集流体包括，但不限于，金属箔、金属圆柱、金属带卷、金属板、金属薄膜、金属板网、冲压金属、发泡金属等。在一实施例中，负极集流体为金属箔。在一实施例中，所述负极集流体为铜箔。如本文所使用，术语“铜箔”包含铜合金箔。
在本申请的实施例中，负极集流体上延伸出负极极耳。
在本申请的实施例中，可以通过裁切负极集流体的方式得到负极极耳。
在本申请的实施例中，本申请的二次电池中的负极极片可使用任何已知方法制备。例如，在负极活性材料中添加导电剂、粘结剂、添加剂与溶剂等，制成浆料，将该浆料涂布在负极集流体上，干燥后通过压制而形成电极。也可以将负极活性物质进行辊成型制成片状电极，或通过压缩成型制成颗粒电极。
在本申请的实施例中，所述正极极耳的数量为N c个，所述负极极耳的数量为N a个，满足：N a>N c，
其中，所述正极极耳的数量N c个满足：2≤N c≤100。即所述正极极耳的数量N c个可以控制在2个～100个范围内。比如，所述正极极耳的数量N c个可以为2个、10个、20个、30个、40个、50个、60个、70个、80个、90个、100个中的一者或其中任意二者组成的范围。值得说明的是，该数量N c个的具体数值仅是示例性地给出，只要数量N c个在2个～100个范围内的任意值均在本申请的保护范围内。
其中，所述负极极耳的数量N a个满足：4≤N a≤102。即负极极耳的数量N a个可以控制在4个～102个范围内。比如，负极极耳的数量N a个可以为4个、12个、22个、32个、42个、52个、62个、72个、82个、92个、102个中的一者或其中任意二者组成的范围。值得说明的是，该数量N a个的具体数值仅是示例性地给出，只要数量N a个在4个～102个范围内的任意值均在本申请的保护范围内。
在本申请的实施例中，所述正极极耳的数量N c与所述负极极耳的数量N a还满足：N a-N c≥2。
可以理解的，本申请中通过正极极耳的数量N c与负极极耳的数量N a之间的关系满足上述范围，以调节正极极耳与负极极耳的数量，控制负极极耳的数量大于正极极耳的数量，从而改善正极的极化，提升正极活性材料的稳定性，从而改善二次电池的循环性能。
在本申请的实施例中，所述正极活性材料层的厚度为H cμm，所述负极活性材料层的厚度为H aμm，满足：H a≤H c，
其中，所述负极活性材料层的厚度H a满足：30≤H a≤250。即负极活性材料层的厚度H aμm可以控制在30 μm～250 μm范围内。比如，负极活性材料层的厚度H aμm可以为30 μm、50 μm、70 μm、90 μm、110 μm、130 μm、150 μm、170 μm、190 μm、210 μm、230 μm、250 μm中的一者或其中任意二者组成的范围。值得说明的是，该厚度H aμm的具体数值仅是示例性地给出，只要厚度H a μm在30 μm～250 μm范围内的任意值均在本申请的保护范围内。在本申请中H c、H a指的是活性材料层的总厚度，即为位于集流体两面的活性材料层的厚度之和。本申请中通过将负极活性材料层的厚度H a控制在上述范围，以对负极活性材料层的厚度进行优化设计，以平衡正负极材料锂离子的脱嵌速率，以维持二次电池在工作过程中电化学反应的平衡，提升二次电池的循环寿命及存储寿命。
其中，所述正极活性材料层的厚度H cμm满足：50≤H c≤400。即正极活性材料层的厚度H cμm可以控制在50μm～400 μm个范围内。比如，负活性材料层的厚度H c可以为50 μm、100 μm、150 μm、200 μm、250 μm、300 μm、350 μm、400μm中的一者或其中任意二者组成的范围。值得说明的是，该厚度H c的具体数值仅是示例性地给出，只要厚度H cμm在50μm～400 μm个范围内的任意值均在本申请的保护范围内。本申请中通过将正极活性材料层的厚度H c控制在上述范围，以对正极活性材料层的厚度进行优化设计，以平衡正负极材料锂离子的脱嵌速率，以维持二次电池在工作过程中电化学反应的平衡，提升二次电池的循环寿命及存储寿命。
在本申请的实施例中，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a还满足：1.0≤H c/H a≤2.0。即正极活性材料层的厚度H c与负极活性材料层的厚度H a的比值可以控制在1.0～2.0范围内。比如，正极活性材料层的厚度H c与负极活性材料层的厚度H a的比值可以为1.0、1.1、1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9、2.0中的一者或其中任意二者组成的范围。值得说明的是，该比值的具体数值仅是示例性地给出，只要比值在1.0～2.0范围内的任意值均在本申请的保护范围内。
可以理解的，本申请中通过将正极活性材料层的厚度H c与负极活性材料层的厚度H a之间的关系控制在上述范围，以平衡正负极材料锂离子的脱嵌速率，以维持二次电池在工作过程中电化学反应的平衡，提升二次电池的循环寿命及存储寿命。
在本申请的实施例中，所述二次电池的设计CB值为0.8~1.1；即二次电池的设计CB值可以控制在0.8~1.1范围内。比如，二次电池的设计CB值可以为0.8、0.85、0.9、0.95、1.0、1.05、1.1中的一者或其中任意二者组成的范围。
其中，设计CB值为单位面积负极极片容量与单位面积正极极片容量的容量比。
在本申请的实施例中，计算设计CB值时需保持正负极片的单位面积相等。
在本申请的实施例中，二次电池在工作过程中采用定容的方式进行充电使得正极极片只释放部分锂离子，多余的锂离子作为储备以补充二次电池在工作过程中活力锂的损失。
可以理解的，本申请中通过将二次电池的设计CB值控制在上述范围，以对二次电池的正极极片进行锂离子富余过量设计，使得二次电池的正极极片内存储有大量备用的活力锂，增加二次电池的正极极片的可逆容量，以对二次电池在循环及存储过程中活性锂的损失进行补充，维持整个二次电池体系的工作过程中的电化学反应的平衡，以提升二次电池的循环寿命及存储寿命；同时本申请中通过对二次电池的正极极片进行锂离子富余过量设计，使得二次电池在循环过程中脱锂深度低，二次电池的极化及阻力小，从而提升了二次电池的能量效率。
在本申请的实施例中，所述二次电池的设计CB值的测试方法为：
S1、获取单位面积负极极片容量：将单位面积的负极极片的其中一面的负极活性物质保留，与锂片、隔膜、电解液组装成扣式电池，0.1C放电至0.005V，0.05mA放电至0.005V，0.02mA放电至0.005V，0.1C充电至2V，所得充电容量即为单位面积负极极片容量；
S2、获取单位面积正极极片容量：将单位面积的正极极片的其中一面的正极活性物质保留，与锂片、隔膜、电解液组装成扣式电池，0.1C充电到4.35V，恒压至50μA，0.1C放电至2.0V，所得放电克容量即为单位面积正极极片容量；
S3、依据步骤S1和步骤S2得到的单位面积负极极片容量和单位面积正极极片容量，计算两者的比值即得到设计CB值。
在本申请的实施例中，二次电池在1C条件下的容量n 1、二次电池在0%SOC条件下的内阻R以及设计CB值之间满足：25≤n 1×R/CB≤100。
可以理解的，本申请中通过限定n 1、R及设计CB值之间满足25≤n 1×R/CB≤100的关系，以对二次电池在1C条件下的容量n 1、二次电池在0%SOC条件下的内阻R以及设计CB值之间的关系进行优化，以此平衡正负极片中的正负极活性材料的锂离子脱嵌速率，以维持整个二次电池体系的工作过程中的电化学反应的平衡，进而提升二次电池的能量效率，最终提升二次电池的循环寿命及存储寿命。
在本申请的实施例中，所述二次电池的实际使用CB’值为1.1~1.3。即二次电池的实际使用CB’值可以控制在1.1~1.3个范围内。比如，二次电池的实际使用CB’值可以为1.1、1.12、1.14、1.16、1.18、1.2、1.22、1.24、1.26、1.28、1.3中的一者或其中任意二者组成的范围。值得说明的是，该实际使用CB’值的具体数值仅是示例性地给出，只要实际使用CB’值在1.1~1.3范围内的任意值均在本申请的保护范围内。
可以理解的，本申请中通过将二次电池的实际使用CB’值控制在上述范围内，以使得二次电池在实际使用的工作过程中不会产生析锂现象，从而减少甚至避免了二次电池在实际使用的工作过程中对活力锂的消耗，提升了二次电池的寿命。
在本申请的实施例中，本申请的二次电池中的使用的电解液包括电解质和溶解该电解质的溶剂。
本申请中对电解质没有特别限制，可以任意地使用作为电解质公知的物质，只要不损害本申请的效果即可。在二次电池的情况下，通常使用锂盐。在本申请的实施例中，所述电解质包括，但不限于，LiPF 6。
同时，本申请中对电解质含量没有特别限制，只要不损害本申请的效果即可。例如可以为0.8mol/L~2.2mol/L。
本申请中对溶剂没有特别限制，可以任意地使用作为溶剂公知的物质，只要不损害本申请的效果即可。
在本申请的实施例中，所述溶剂包括，但不限于，碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸二乙酯(DEC)、碳酸甲乙酯（EMC）、碳酸二甲酯（DMC）、碳酸丁烯酯（BC）和甲基乙烯碳酸（MEC）。上述溶剂可单独使用或任意组合使用。
在本申请的实施例中，为了防止短路，在正极与负极之间通常设置有隔离膜。这种情况下，本申请的电解液通常渗入该隔离膜而使用。
本申请中对隔离膜的材料、形状、厚度、孔隙率及平均孔径没有特别限制，只要不损害本申请的效果即可。
另一方面，在本申请的实施例中，本申请还提供了一种用电装置，包括如上述任一项所述的二次电池，所述二次电池作为所述用电装置的供电电源。
其中，所述用电装置包括电动车、储能电池等。
下面以锂离子电池为例并且结合具体的实施例说明锂离子电池的制备，本领域的技术人员将理解，本申请中描述的制备方法仅是实施例，其他任何合适的制备方法均在本申请的范围内。
以下说明根据本申请的锂离子电池的实施例和对比例进行性能评估。
实施例1
一、锂离子电池的制备
1、正极极片的制备
将正极活性材料磷酸铁锂、导电剂为导电炭黑SP、粘结剂为PVDF按照质量比97：0.7：2.3进行混合，之后加入NMP作为溶剂进行混合，搅拌一定时间后获得具有一定流动性的均匀正极浆料；将正极浆料均匀双面涂覆在正极集流体涂炭铝箔上，随后转移至120℃烘箱进行干燥，然后经过辊压、分条、裁片后得到正极极片。
2、负极极片的制备
将负极活性材料石墨、导电剂为导电炭黑SP、增稠剂为CMC、粘结剂为SBR按照质量比96.5：0.5：1.2：1.8进行混合，之后加入去离子水作为溶剂进行混合，搅拌一定时间后获得具有一定流动性的均匀负极浆料；将负极浆料均匀双面涂覆在负极集流体铜箔上，随后转移至110℃烘箱进行干燥，然后经过辊压、分条、裁片得到负极极片。
3、电解液的制备
将碳酸乙烯酯（EC）、碳酸甲乙酯（EMC）、碳酸二乙酯（DEC）按照体积比1:1:1混合，然后加入1mol/L的LiPF 6混合均匀，配制成电解液。
4、隔离膜的制备
以PP膜作为隔离膜。
5、锂离子电池的制备
采用上述步骤制备出的负极极片、正极极片经过干燥后，与隔离膜一起采用卷绕机制备出卷绕电芯，将正极极耳与负极极耳焊接在电芯顶盖上，并将焊接完成的带顶盖电芯放入铝壳中进行封装；经过灌注电解液、化成定容制得锂离子电池。
其中，实施例1中的锂离子电池在1C条件下的容量n 1 Ah为5Ah，在0%SOC条件下的内阻R mΩ为18 mΩ，n 1和R之间满足：n 1×R =90，所述正极极耳的数量N c为2个，所述负极极耳的数量N a为4个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c =2个，所述正极活性材料层的厚度H cμm为50μm，所述负极活性材料层的厚度H aμm为30μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a =1.67，所述二次电池的设计CB值为1.1，n 1、R以及设计CB值之间满足：81.8，所述二次电池的实际使用CB’值为1.1。
二、测试方法
1、锂离子电池循环性能的测试方法
在25℃下，将制备得到的锂离子电池以1C倍率恒容充电至标称容量、以1C倍率放电至2.5V，进行循环测试，直至锂离子二次电池的容量衰减至初始容量的80％，记录循环圈数。
2、锂离子电池高温循环性能的测试方法
在25℃下，将制备得到的锂离子电池以1C倍率充电至标称容量、以1C倍率放电至2.5V，获得电池的初始容量。将电池1C倍率满充后，将电池置于60℃的恒温箱中保存，直至锂离子二次电池的容量衰减至初始容量的80％，记录存储的天数。
3、锂离子电池能量效率的测试方法
在25℃下，将制备得到的锂离子电池以1C恒流充电至电池的标称容量，记录为充电能量E 1，静置30min，然后以1C恒流放电至电压下限（2.5V），记录为放电能量E 2，计算锂离子电池的能量效率值E 2/ E 1。
实施例2
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1Ah为50Ah，在0%SOC条件下的内阻R mΩ为0.6 mΩ，n 1和R之间满足：n 1×R=30，所述二次电池的设计CB值为1.07，n 1、R以及设计CB值之间满足：n 1×R/CB =28，所述二次电池的实际使用CB’值为1.12。
实施例3
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为100Ah，在0%SOC条件下的内阻R mΩ为0.37 mΩ，n 1和R之间满足：n 1×R=37，所述二次电池的设计CB值为1.04，n 1、R以及设计CB值之间满足：n 1×R/CB=35.6，所述二次电池的实际使用CB’值为1.14。
实施例4
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为150Ah，在0%SOC条件下的内阻R mΩ为0.31 mΩ，n 1和R之间满足：n 1×R=46.5，所述二次电池的设计CB值为1.01，n 1、R以及设计CB值之间满足：n 1×R/CB=46，所述二次电池的实际使用CB’值为1.16。
实施例5
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1Ah为200Ah，在0%SOC条件下的内阻R mΩ为0.28mΩ，n 1和R之间满足：n 1×R=56，所述二次电池的设计CB值为0.98，n 1、R以及设计CB值之间满足：n 1×R=57.1，所述二次电池的实际使用CB’值为1.18。
实施例6
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1Ah为250Ah，在0%SOC条件下的内阻R mΩ为0.2 mΩ，n 1和R之间满足：n 1×R=50，所述二次电池的设计CB值为0.95，n 1、R以及设计CB值之间满足：n 1×R/CB=52.6，所述二次电池的实际使用CB’值为1.2。
实施例7
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为300Ah，在0%SOC条件下的内阻R mΩ为0.18mΩ，n 1和R之间满足：n 1×R=54，所述二次电池的设计CB值为0.92，n 1、R以及设计CB值之间满足：n 1×R/CB=58.7，所述二次电池的实际使用CB’值为1.22。
实施例8
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为350Ah，在0%SOC条件下的内阻R mΩ为0.16mΩ，n 1和R之间满足：n 1×R=56，所述二次电池的设计CB值为0.89，n 1、R以及设计CB值之间满足：n 1×R/CB=62.9，所述二次电池的实际使用CB’值为1.24。
实施例9
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为400Ah，在0%SOC条件下的内阻R mΩ为0.15 mΩ，n 1和R之间满足：n 1×R=60，所述二次电池的设计CB值为0.86，n 1、R以及设计CB值之间满足：n 1×R/CB=69.8，所述二次电池的实际使用CB’值为1.26。
实施例10
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为450Ah，在0%SOC条件下的内阻R mΩ为0.13 mΩ，n 1和R之间满足：n 1×R=58.5，所述二次电池的设计CB值为0.83，n 1、R以及设计CB值之间满足：n 1×R/CB=70.5，所述二次电池的实际使用CB’值为1.28。
实施例11
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为500Ah，在0%SOC条件下的内阻R mΩ为0.12 mΩ，n 1和R之间满足：n 1×R=60，所述二次电池的设计CB值为0.8，n 1、R以及设计CB值之间满足：n 1×R/CB=75.0，所述二次电池的实际使用CB’值为1.3。
实施例12
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为30Ah，在0%SOC条件下的内阻R mΩ为1 mΩ，n 1和R之间满足：n 1×R=30，所述二次电池的设计CB值为1.08，n 1、R以及设计CB值之间满足：n 1×R/CB=27.8，所述二次电池的实际使用CB’值为1.116。
实施例13
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为15Ah，在0%SOC条件下的内阻R mΩ为5 mΩ，n 1和R之间满足：n 1×R=75，所述二次电池的设计CB值为1.085，n 1、R以及设计CB值之间满足：n 1×R/CB=69.1，所述二次电池的实际使用CB’值为1.112。
实施例14
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为8Ah，在0%SOC条件下的内阻R mΩ为10mΩ，n 1和R之间满足：n 1×R=80，所述二次电池的设计CB值为1.09，n 1、R以及设计CB值之间满足：n 1×R/CB=73.4，所述二次电池的实际使用CB’值为1.108。
实施例15
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为6Ah，在0%SOC条件下的内阻R mΩ为15mΩ，n 1和R之间满足：n 1×R=90，所述二次电池的设计CB值为1.095，n 1、R以及设计CB值之间满足：n 1×R/CB=82.2，所述二次电池的实际使用CB’值为1.104。
实施例1~15可以通过调整正极活性材料磷酸铁锂的含量来控制锂离子电池的容量n 1，通过控制容量和调整正极极片和/或负极极片导电炭黑的含量控制锂离子电池的内阻R，以获得实施例1~15对应的锂离子电池。
实施例16
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极极耳的数量N c为12个，所述负极极耳的数量N a为14个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c=2个，所述二次电池的设计CB值为1.08，所述二次电池的实际使用CB’值为1.11。
实施例17
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极极耳的数量N c为22个，所述负极极耳的数量N a为26个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c=4个，所述二次电池的设计CB值为1.05，所述二次电池的实际使用CB’值为1.13。
实施例18
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极极耳的数量N c为32个，所述负极极耳的数量N a为38个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c=6个，所述二次电池的设计CB值为1.02，所述二次电池的实际使用CB’值为1.15。
实施例19
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极极耳的数量N c为42个，所述负极极耳的数量N a为46个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c=4个，所述二次电池的设计CB值为0.99，所述二次电池的实际使用CB’值为1.17。
实施例20
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极极耳的数量N c为52个，所述负极极耳的数量N a为58个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c=6个，所述二次电池的设计CB值为0.96，所述二次电池的实际使用CB’值为1.19。
实施例21
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极极耳的数量N c为62个，所述负极极耳的数量N a为64个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c=2个，所述二次电池的设计CB值为0.93，所述二次电池的实际使用CB’值为1.21。
实施例22
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极极耳的数量N c为72个，所述负极极耳的数量N a为74个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c=2个，所述二次电池的设计CB值为0.9，所述二次电池的实际使用CB’值为1.23。
实施例23
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极极耳的数量N c为82个，所述负极极耳的数量N a为86个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c=4个，所述二次电池的设计CB值为0.87，所述二次电池的实际使用CB’值为1.25。
实施例24
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极极耳的数量N c为92个，所述负极极耳的数量N a为94个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c=2个，所述二次电池的设计CB值为0.84，所述二次电池的实际使用CB’值为1.27。
实施例25
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极极耳的数量N c为100个，所述负极极耳的数量N a为102个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c=2个，所述二次电池的设计CB值为0.8，所述二次电池的实际使用CB’值为1.3。
实施例26
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极极耳的数量N c为1个，所述负极极耳的数量N a为2个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c=1，所述二次电池的设计CB值为1.14，所述二次电池的实际使用CB’值为1.09。
实施例27
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极极耳的数量N c为101个，所述负极极耳的数量N a为100个，所述正极极耳的数量N c与所述负极极耳的数量N a满足：N a-N c=-1，所述二次电池的设计CB值为0.78，所述二次电池的实际使用CB’值为1.32。
实施例16~27可以通过调整正极极耳与负极极耳的焊接数量来获得对应的锂离子电池。
实施例28
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极活性材料层的厚度H cμm为70μm，所述负极活性材料层的厚度H aμm为50μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a=1.4，所述二次电池的设计CB值为1.085，所述二次电池的实际使用CB’值为1.105。
实施例29
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极活性材料层的厚度H cμm为80μm，所述负极活性材料层的厚度H aμm为80μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a=1.00，所述二次电池的设计CB值为1.055，所述二次电池的实际使用CB’值为1.125。
实施例30
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极活性材料层的厚度H cμm为120μm，所述负极活性材料层的厚度H aμm为100μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a=1.20，所述二次电池的设计CB值为1.025，所述二次电池的实际使用CB’值为1.145。
实施例31
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极活性材料层的厚度H cμm为150μm，所述负极活性材料层的厚度H aμm为120μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a=1.25，所述二次电池的设计CB值为0.995，所述二次电池的实际使用CB’值为1.165。
实施例32
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极活性材料层的厚度H cμm为190μm，所述负极活性材料层的厚度H aμm为140μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a=1.36，所述二次电池的设计CB值为0.965，所述二次电池的实际使用CB’值为1.185。
实施例33
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极活性材料层的厚度H cμm为235μm，所述负极活性材料层的厚度H aμm为160μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a=1.47，所述二次电池的设计CB值为0.935，所述二次电池的实际使用CB’值为1.205。
实施例34
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极活性材料层的厚度H cμm为360μm，所述负极活性材料层的厚度H aμm为180μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a=2.00，所述二次电池的设计CB值为0.905，所述二次电池的实际使用CB’值为1.225。
实施例35
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极活性材料层的厚度H cμm为350μm，所述负极活性材料层的厚度H aμm为200μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a=1.75，所述二次电池的设计CB值为0.875，所述二次电池的实际使用CB’值为1.245。
实施例36
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极活性材料层的厚度H cμm为370μm，所述负极活性材料层的厚度H aμm为230μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a=1.61，所述二次电池的设计CB值为0.845，所述二次电池的实际使用CB’值为1.265。
实施例37
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极活性材料层的厚度H cμm为400μm，所述负极活性材料层的厚度H aμm为250μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a=1.67，所述二次电池的设计CB值为0.8，所述二次电池的实际使用CB’值为1.30。
实施例38
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极活性材料层的厚度H cμm为70μm，所述负极活性材料层的厚度H aμm为30μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a=2.3，所述二次电池的设计CB值为1.16，所述二次电池的实际使用CB’值为1.08。
实施例39
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
所述正极活性材料层的厚度H cμm为240μm，所述负极活性材料层的厚度H aμm为260μm，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a满足：H c/H a=0.92，所述二次电池的设计CB值为0.77，所述二次电池的实际使用CB’值为1.32。
实施例28~39可以通过调整正极活性材料层与负极活性材料层的涂布厚度来获得对应的锂离子电池。
对比例1
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为4Ah，在0%SOC条件下的内阻R mΩ为28 mΩ，n 1和R之间满足：n 1×R=112，所述二次电池的设计CB值为1.12，n 1、R以及设计CB值之间满足：n 1×R/CB=100.0，所述二次电池的实际使用CB’值为1.08。
对比例2
依照实施例1的方法制备锂离子电池，同时按照实施例1中的测试方法测试锂离子电池，除以下不同之处：
锂离子电池在1C条件下的容量n 1 Ah为60Ah，在0%SOC条件下的内阻R mΩ为0.03 mΩ，n 1和R之间满足：n 1×R=18，所述二次电池的设计CB值为0.79，n 1、R以及设计CB值之间满足：n 1×R/CB=22.8，所述二次电池的实际使用CB’值为1.31。
三、测试结果
表1 实施例1~15的参数及对比例1~2的参数及测试结果
  n1 R n1×R 设计CB值 n1×R/CB 实际使用CB’值 25℃能量效率 25℃循环寿命(圈) 60℃存储寿命（天）
实施例1 5 18 90 1.1 81.8 1.1 93.20% 4117 430
实施例2 50 0.6 30 1.07 28.0 1.12 93.29% 4532 515
实施例3 100 0.37 37 1.04 35.6 1.14 93.32% 4987 575
实施例4 150 0.31 46.5 1.01 46.0 1.16 93.35% 5515 635
实施例5 200 0.28 56 0.98 57.1 1.18 93.42% 5951 695
实施例6 250 0.2 50 0.95 52.6 1.2 93.61% 6322 740
实施例7 300 0.18 54 0.92 58.7 1.22 94.03% 6768 785
实施例8 350 0.16 56 0.89 62.9 1.24 94.17% 7015 815
实施例9 400 0.15 60 0.86 69.8 1.26 94.39% 7418 845
实施例10 450 0.13 58.5 0.83 70.5 1.28 94.50% 7816 875
实施例11 500 0.12 60 0.8 75.0 1.3 94.33% 8361 890
实施例12 30 1 30 1.08 27.8 1.116 93.28% 4421 509
实施例13 15 5 75 1.085 69.1 1.112 93.25% 4378 487
实施例14 8 10 80 1.09 73.4 1.108 93.26% 4310 467
实施例15 6 15 90 1.095 82.2 1.104 93.24% 4233 445
对比例1 4 28 112 1.12 100.0 1.08 88.10% 2240 250
对比例2 600 0.03 18 0.79 22.8 1.31 88.90% 3009 315
结果分析：本申请采用较低的设计CB值和正常的使用CB值，以使得正极的活性锂富余，以此补充二次电池在工作过程中的活性锂损失；并通过限定二次电池容量、二次电池的内阻，同时限定二次电池容量、内阻与设计CB值之间的关系，以此平衡正负极极片的锂离子脱嵌速率，使整个二次电池体系工作过程中电化学反应平衡达到最佳，从而提升二次电池的能量效率和寿命。相比于对比例，本申请在25℃循环寿命、60℃存储寿命和25℃能量效率均有明显提升。
表2  实施例1及实施例16~27的参数及测试结果
  Nc（个） Na（个） Na-Nc（个） 设计CB值 实际使用CB’值 25℃能量效率 25℃循环寿命（圈） 60℃存储寿命（天）
实施例1 2 4 2 1.1 1.1 93.20% 4117 430
实施例16 12 14 2 1.08 1.11 93.15% 4416 485
实施例17 22 26 4 1.05 1.13 93.19% 4828 560
实施例18 32 38 6 1.02 1.15 93.23% 5296 590
实施例19 42 46 4 0.99 1.17 93.28% 5843 665
实施例20 52 58 6 0.96 1.19 93.48% 6017 725
实施例21 62 64 2 0.93 1.21 93.91% 6547 785
实施例22 72 74 2 0.9 1.23 94.03% 6687 800
实施例23 82 86 4 0.87 1.25 94.26% 7304 815
实施例24 92 94 2 0.84 1.27 94.38% 7559 860
实施例25 100 102 2 0.8 1.3 94.19% 8174 875
实施例26 1 2 1 1.14 1.09 91.97% 3825 335
实施例27 101 100 -1 0.78 1.32 92.76% 3995 400
结果分析：本发明采用较低的设计CB值和正常的使用CB值，以使得正极的活性锂富余，以此补充二次电池在工作过程中的活性锂损失；并通过限定二次电池的正负极极耳的数量及正负极极耳数量的差值，以此平衡正负极极片的锂离子脱嵌速率，使整个二次电池体系工作过程中电化学反应平衡达到更优状态，从而提升二次电池的能量效率和寿命。相比于对比例，本申请在25℃循环寿命、60℃存储寿命和25℃能量效率均有明显提升。
表3  实施例1及实施例28~39的参数及测试结果
  Ha Hc Hc/Ha n1 R n1×R 设计CB值 实际使用CB’值 25℃能量效率 25℃循环寿命（圈） 60℃存储寿命（天）
实施例1 30 50 1.67 5 18 90 1.1 1.1 93.20% 4117 430
实施例28 50 70 1.40 7 12 84 1.085 1.105 93.01% 4433 485
实施例29 80 80 1.00 9 9 81 1.055 1.125 93.06% 4852 575
实施例30 100 120 1.20 11 8 88 1.025 1.145 93.11% 5329 620
实施例31 120 150 1.25 12 6 72 0.995 1.165 93.14% 5859 680
实施例32 140 190 1.36 14 5 70 0.965 1.185 93.35% 6063 755
实施例33 160 235 1.47 17 4 68 0.935 1.205 93.79% 6580 800
实施例34 180 360 2.00 21 3 63 0.905 1.225 93.89% 6736 800
实施例35 200 350 1.75 22 2.5 55 0.875 1.245 94.13% 7321 830
实施例36 230 370 1.61 24 2 48 0.845 1.265 94.26% 7598 890
实施例37 250 400 1.60 26 1.5 39 0.8 1.30 94.05% 8202 890
实施例38 30 70 2.3 6 15 90 1.16 1.08 91.84% 3787 350
实施例39 260 240 0.92 18 3.5 63 0.77 1.32 92.62% 3972 430
结果分析：本申请采用较低的设计CB值和正常的实际使用CB’值，以使得正极的活性锂富余，以此补充二次电池在工作过程中的活性锂损失；并通过限定二次电池的正负极极片的厚度及正负极极片的厚度的比值，以此平衡正负极极片的锂离子脱嵌速率，使整个二次电池体系工作过程中电化学反应平衡达到最佳，从而提升二次电池的能量效率和寿命。相比于对比例，本申请在25℃循环寿命、60℃存储寿命和25℃能量效率均有明显提升。
以上步骤所提供的介绍，只是用于帮助理解本申请的方法、结构及核心思想。对于本技术领域内的普通技术人员来说，在不脱离本申请原理的前提下，还可以对本申请进行若干改进和修饰，这些改进和修饰也同样属于本申请权利要求保护范围之内。

Claims (10)

  1. 一种二次电池，其特征在于，所述二次电池在1C条件下的容量为n 1 Ah，所述二次电池在0%SOC条件下的内阻为R mΩ，n 1和R之间满足：30≤n 1×R≤90，其中5≤n 1≤500，0.05≤R≤18。
  2. 根据权利要求1所述的二次电池，其特征在于，所述二次电池包括正极极片和负极极片，所述正极极片包括正极集流体、设置于所述正极集流体上的正极活性材料层、以及从所述正极集流体上延伸出的正极极耳，所述正极活性材料层包含磷酸铁锂；所述负极极片包括负极集流体、设置于所述负极集流体上的负极活性材料层、以及从所述负极集流体上延伸出的负极极耳，所述负极活性材料层包含石墨。
  3. 根据权利要求2所述的二次电池，其特征在于，所述正极极耳的数量为N c个，所述负极极耳的数量为N a个，满足：N a>N c，其中2≤N c≤100，4≤N a≤102。
  4. 根据权利要求3所述的二次电池，其特征在于，所述正极极耳的数量N c与所述负极极耳的数量N a还满足：N a-N c≥2。
  5. 根据权利要求2所述的二次电池，其特征在于，所述正极活性材料层的厚度为H cμm，所述负极活性材料层的厚度为H aμm，满足：H a≤H c，其中，30≤H a≤250，50≤H c≤400。
  6. 根据权利要求5所述的二次电池，其特征在于，所述正极活性材料层的厚度H c与所述负极活性材料层的厚度H a还满足：1.0≤H c/H a≤2.0。
  7. 根据权利要求1所述的二次电池，其特征在于，所述二次电池的设计CB值为0.8~1.1；
    其中，设计CB值为单位面积负极极片容量与单位面积正极极片容量的容量比。
  8. 根据权利要求7所述的二次电池，其特征在于，n 1、R以及设计CB值之间满足：25≤n 1×R/CB≤100。
  9. 根据权利要求1-8任一项所述的二次电池，其特征在于，所述二次电池的实际使用CB’值为1.1~1.3。
  10. 一种用电装置，其特征在于，包括如权利要求1~9任一项所述的二次电池，所述二次电池作为所述用电装置的供电电源。
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