WO2023045111A1 - 二次电池电极锂枝晶在线监测方法及系统、二次电池 - Google Patents

二次电池电极锂枝晶在线监测方法及系统、二次电池 Download PDF

Info

Publication number
WO2023045111A1
WO2023045111A1 PCT/CN2021/137619 CN2021137619W WO2023045111A1 WO 2023045111 A1 WO2023045111 A1 WO 2023045111A1 CN 2021137619 W CN2021137619 W CN 2021137619W WO 2023045111 A1 WO2023045111 A1 WO 2023045111A1
Authority
WO
WIPO (PCT)
Prior art keywords
secondary battery
lithium
battery
piezoelectric
piezoelectric sensing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2021/137619
Other languages
English (en)
French (fr)
Inventor
薛冬峰
彭超
王晓明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Institute of Advanced Technology of CAS
Original Assignee
Shenzhen Institute of Advanced Technology of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Institute of Advanced Technology of CAS filed Critical Shenzhen Institute of Advanced Technology of CAS
Publication of WO2023045111A1 publication Critical patent/WO2023045111A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/68—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using electric discharge to ionise a gas
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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 technical field of batteries, and in particular relates to a method and system for on-line monitoring of lithium dendrites in electrodes of secondary batteries, and a secondary battery.
  • lithium-ion secondary batteries have been widely used in various portable electronic devices, electrical appliances, and new energy vehicles. Extensive use has higher requirements on the performance of the battery, especially the safety performance.
  • Lithium dendrites one of the safety hazards of lithium-ion secondary batteries, are deposits formed by the uneven deposition of lithium ions on the surface of the negative electrode during the charge-discharge cycle of the lithium negative electrode. Lithium dendrites are constantly forming, growing, or breaking down as the battery is used. The broken dendrite loses its activity and no longer contributes to the battery capacity; while the growing lithium dendrite will pierce the separator and cause a short circuit of the battery, resulting in thermal runaway.
  • the early warning and protection systems designed for the safety of lithium-ion batteries are mostly based on ultrasonic or X-ray thermal sensors, smoke sensors or infrared sensors.
  • the technical solution of online monitoring whether it is ultrasonic or internal resistance test, has certain disadvantages.
  • the requirements for testing instruments, testing environment, and cost are relatively high, making it difficult to apply them in large-scale commercial applications.
  • by testing the internal resistance or disassembling the battery for inspection it is necessary to stop the test, which is very inconvenient during use. Therefore, the development of online monitoring and early warning system is very necessary.
  • the on-line monitoring method and system for lithium dendrites include: through the application of the three-electrode test system in the early stage to detect the lithium analysis of the battery under the test condition, and accurately mark the starting capacity position of the lithium analysis under the test condition through the negative electrode potential and continuous capacity, and correspond to the terminal voltage of the lithium-ion battery.
  • it is only necessary to detect the terminal voltage under actual working conditions, and convert it to the negative electrode potential through the system, and detect the lithium analysis status of the lithium-ion battery in real time to monitor the formation of lithium dendrites.
  • the limitations of this method are: (1) In the early stage, the test items need to be designed and tested according to the actual application status; (2) There may be differences between the actual application status and the test environment.
  • the purpose of this application is to provide a secondary battery electrode lithium dendrite online monitoring method and system, as well as a secondary battery, which aims to solve the difficulty of online timely and accurate generation of electrode lithium dendrites in existing secondary batteries to a certain extent detection problem.
  • the present application provides a method for on-line monitoring of lithium dendrites in a secondary battery electrode, comprising the following steps:
  • a piezoelectric sensing layer is arranged between the electrode sheet and the diaphragm of the secondary battery; the piezoelectric sensing layer is electrically connected to the early warning detection system;
  • the early warning detection system monitors the voltage signal generated by the piezoelectric induction layer in the battery in real time;
  • the growth condition of the lithium dendrite is judged by the voltage signal, and the safety condition of the secondary battery is obtained.
  • the material of the piezoelectric sensing layer includes: at least one piezoelectric sensing material among lithium niobate, lithium tantalate, barium titanate, and lead titanate.
  • the thickness of the piezoelectric sensing layer is 10-15 ⁇ m.
  • the step of arranging the piezoelectric sensing layer between the electrode sheet and the diaphragm of the secondary battery includes: preparing the piezoelectric sensing layer by using a pulsed laser deposition method; bonding the piezoelectric sensing layer on the the surface of the diaphragm.
  • the early warning detection system detects that the voltage signal range is 150 When ⁇ 400 pC/N, a potential safety hazard alarm is issued and the battery stops operating.
  • an inert thin film layer is further provided between the piezoelectric induction layer and the electrode sheet, and the inert thin film layer has ion migration performance.
  • the thickness of the inert film layer is 3-8 ⁇ m.
  • the material of the inert film layer includes: at least one of silicon oxide, lithium carbonate, lithium germanium aluminum phosphate, and lithium titanium aluminum phosphate.
  • the electrode sheets are selected from negative electrode sheets.
  • the present application provides an online monitoring system for lithium dendrites of secondary battery electrodes.
  • the online monitoring system for lithium dendrites of secondary battery electrodes includes: a battery unit, a piezoelectric sensing unit, and an early warning detection unit.
  • the piezoelectric The sensing unit is arranged between the electrode sheet and the diaphragm of the battery unit, and the piezoelectric sensing unit is electrically connected to the early warning detection unit.
  • the piezoelectric sensing unit includes: at least one of a lithium niobate sensing unit, a lithium tantalate sensing unit, a barium titanate sensing unit, and a lead titanate sensing unit.
  • the thickness of the piezoelectric sensing unit is 10-15 ⁇ m.
  • the range detection range of the voltage signal by the early warning detection unit is 50 ⁇ 500 pC/N.
  • the present application provides a secondary battery.
  • the secondary battery includes a piezoelectric sensing layer disposed between an electrode sheet and a diaphragm, and the piezoelectric sensing layer is electrically connected to an early warning detection system.
  • the method for on-line monitoring of lithium dendrites in secondary battery electrodes includes setting a piezoelectric sensing layer between the electrode sheet and the diaphragm, and the piezoelectric sensing layer is electrically connected to the early warning detection system, and the charging and discharging operation of the battery cycle During the process, when the piezoelectric sensing layer is subjected to the physical pressure generated by the growth of lithium dendrites, electric polarization will occur inside the piezoelectric sensing layer, which will cause the surface of the medium to be charged, and then generate a voltage signal.
  • the early warning monitoring system can monitor the voltage signal generated by the piezoelectric sensing layer in the battery in real time.
  • a piezoelectric sensing layer is set between the battery diaphragm and the electrode sheet.
  • the electrical signal is released through the circuit Transmission to the early warning detection system can directly monitor the safety status of the early warning battery in real time, without the need for pre-simulation environment testing, and without dismantling the battery for detection.
  • the online monitoring method is flexible and convenient to operate, and has high detection accuracy, low cost, and easy scale. application.
  • the second aspect of the present application provides the secondary battery electrode lithium dendrite online monitoring system, the battery unit, the early warning detection unit and the piezoelectric sensing unit arranged between the electrode sheet and the diaphragm of the battery unit, the piezoelectric sensing unit and the piezoelectric sensing unit
  • the early warning detection unit is electrically connected.
  • the change of the voltage signal of the piezoelectric sensing unit is monitored in real time through the early warning detection unit, so as to monitor the growth of lithium dendrites in the battery unit in real time.
  • the voltage signal increases, it indicates the stress of lithium dendrites on the gas production of the piezoelectric sensing layer at this time Larger lithium dendrites have the risk of piercing the diaphragm, and the early warning monitoring unit sends early warning information in time to ensure the safety performance of the battery unit.
  • the secondary battery provided in the third aspect of the present application since a piezoelectric sensing layer is provided between the electrode sheet and the diaphragm, and the piezoelectric sensing layer is electrically connected to the early warning detection system, during the operation of the battery, the piezoelectric sensing layer
  • the growth of lithium dendrites in the battery can be monitored in real time, thereby monitoring the safety status of the battery in real time. Therefore, the secondary battery provided by the present application has high safety, good controllability and wide application prospect.
  • Fig. 1 is a schematic structural diagram of the secondary battery electrode lithium dendrite online monitoring system provided in Example 1 of the present application;
  • Fig. 2 is a schematic structural diagram of an online lithium dendrite monitoring system for a secondary battery electrode provided in Example 2 of the present application.
  • the term "and/or” describes the association relationship of associated objects, indicating that there may be three relationships, for example, A and/or B may mean: A exists alone, A and B exist simultaneously, and B exists alone Condition. Among them, A and B can be singular or plural.
  • the character "/" generally indicates that the contextual objects are an "or" relationship.
  • At least one means one or more, and “multiple” means two or more.
  • At least one of the following” or similar expressions refer to any combination of these items, including any combination of single or plural items.
  • “at least one (one) of a, b, or c”, or “at least one (one) of a, b, and c” can mean: a, b, c, a-b (that is, a and b), a-c, b-c, or a-b-c, where a, b, c can be single or multiple.
  • sequence numbers of the above-mentioned processes do not mean the order of execution, and some or all steps may be executed in parallel or sequentially, and the execution order of each process shall be based on its functions and The internal logic is determined and should not constitute any limitation to the implementation process of the embodiment of the present application.
  • the weight of the relevant components mentioned in the description of the embodiments of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the various components.
  • the scaling up or down of the content of the fraction is within the scope disclosed in the description of the embodiments of the present application.
  • the mass in the description of the embodiments of the present application may be ⁇ g, mg, g, kg and other well-known mass units in the chemical industry.
  • first and second are only used for descriptive purposes to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features.
  • first XX can also be called the second XX
  • second XX can also be called the first XX.
  • a feature defined as “first” and “second” may explicitly or implicitly include one or more of these features.
  • the first aspect of the embodiment of the present application provides an online monitoring method for lithium dendrites in secondary battery electrodes, including the following steps:
  • a piezoelectric induction layer is provided between the electrode sheet and the diaphragm of the secondary battery; the piezoelectric induction layer is electrically connected to the early warning detection system;
  • the early warning detection system monitors the voltage signal generated by the piezoelectric induction layer in the battery in real time;
  • a piezoelectric sensing layer is provided between the electrode sheet and the diaphragm, and the piezoelectric sensing layer is electrically connected to the early warning detection system, and the battery is charged and discharged in cycles.
  • the piezoelectric sensor when the piezoelectric sensing layer is subjected to the physical pressure generated by the growth of lithium dendrites, an electric polarization phenomenon will occur inside the piezoelectric sensing layer, which will cause the surface of the medium to be charged, and then generate a voltage signal.
  • the early warning monitoring system can monitor the voltage signal generated by the piezoelectric sensing layer in the battery in real time.
  • a piezoelectric sensing layer is provided between the battery separator and the electrode sheet.
  • the safety status of the early warning battery can be directly monitored online in real time, without the need for a preliminary simulation environment test, and without disassembling the battery for detection.
  • the online monitoring method is flexible and convenient to operate, and has high detection accuracy and low cost. Easy to scale application.
  • the step of disposing a piezoelectric sensing layer between the electrode sheet and the separator of the secondary battery includes:
  • the piezoelectric sensing layer is prepared by pulsed laser deposition method; it is conducive to the formation of a stable, dense, uniform and flat piezoelectric sensing layer, which is conducive to the more accurate and rapid physical pressure generated by the piezoelectric sensing layer on the growth of lithium dendrites. Induction.
  • the piezoelectric sensing layer is attached to the surface of the diaphragm. By bonding the piezoelectric sensing layer and the diaphragm, the piezoelectric sensing layer can more timely and accurately sense the stress generated by the growth of lithium dendrites on the diaphragm, thereby improving detection sensitivity and accuracy.
  • the material of the piezoelectric sensing layer includes: at least one piezoelectric sensing material among lithium niobate, lithium tantalate, barium titanate, and lead titanate; these materials have good piezoelectric properties and high sensitivity , when physical pressure is applied to these piezoelectric materials, electric polarization occurs inside the material due to the force, causing the surface of the medium to be charged, and then a gas voltage signal is generated. At the same time, these materials also have good ion migration and transport properties, and have little impact on the electrochemical performance of the battery.
  • the sensitivity of these piezoelectric sensing materials used in the piezoelectric sensing layer in the embodiment of the present application to physical pressure is sufficient to ensure the timeliness and accuracy of early warning detection.
  • the piezoelectric sensing layer adopts a lithium niobate layer, which has good piezoelectric properties, about 6 ⁇ 10 ⁇ 12 coulombs/kg cm2, and high sensitivity.
  • the thickness of the piezoelectric sensing layer is 10-15 ⁇ m, which can take into account ion migration and shuttle and piezoelectric sensing effects. If the piezoelectric sensing layer is too thin, it is not conducive to the timely preparation of the physical stress generated by the induction of lithium dendrite growth; Layers also reduce the energy density of the battery. In some specific embodiments, the thickness of the piezoelectric sensing layer may be 10-11 ⁇ m, 11-13 ⁇ m, 13-15 ⁇ m, etc.
  • an inert film layer is further provided between the piezoelectric sensing layer and the electrode sheet, and the inert film layer has ion migration properties.
  • the inert thin film layer provided between the piezoelectric sensing layer and the electrode sheet in the embodiment of the present application can not only isolate the chemical reaction between the electrolyte and the piezoelectric sensing layer, but also has good ion migration and transmission performance, and will not affect the battery. run.
  • the material of the inert film layer includes: at least one of silicon oxide, lithium carbonate, lithium germanium aluminum phosphate, lithium titanium aluminum phosphate, and these materials can block the chemical reaction between the electrolyte and the piezoelectric sensing layer. reaction, but also has high ion mobility.
  • the inert thin film layer adopts a silicon oxide layer, and the inert thin film layer formed by silicon oxide not only has good physical and chemical stability of the film layer, but also can effectively prevent the electrolyte from reacting with the materials in the piezoelectric induction layer, and the formed
  • the membrane layer is rich in micropores, and ions can migrate and transport efficiently.
  • the thickness of the inert thin film layer is 3-8 ⁇ m; this thickness can effectively isolate the contact reaction between the electrolyte solution and the piezoelectric sensing layer, and avoid reducing the energy density of the battery due to excessive thickness of the film layer.
  • the thickness of the inert film layer may be 3-5 ⁇ m, 5-6 ⁇ m, 6-8 ⁇ m, etc.
  • the electrode sheets are selected from negative electrode sheets.
  • the ion reduction reaction mainly occurs at the negative electrode of the battery.
  • lithium ions are reduced at the negative electrode, it is easier to form a dendritic metal lithium element, that is, lithium dendrites. Therefore, the risk of lithium dendrite formation on the surface of the negative electrode is greater, and it is more conducive to testing the safety performance of the battery system if the piezoelectric sensing layer is arranged between the negative electrode and the separator.
  • the piezoelectric sensing layer is electrically connected to the early warning detection system through the conductive line, and the pressure signal is transmitted to the early warning detection system through the conductive line to monitor the growth of lithium dendrites in the battery in real time.
  • the early warning detection system monitors the voltage signal generated by the piezoelectric sensing layer in the battery in real time.
  • the early warning detection system in the embodiment of the present application can detect the growth of lithium dendrites in the battery in real time by monitoring the change of the voltage signal of the piezoelectric induction layer, thereby judging the safety status of the battery.
  • the voltage signal is used to judge the growth of lithium dendrites, so as to obtain the safety status of the secondary battery.
  • the early warning detection system detects that the voltage signal range is 150 ⁇ 400 pC/N, it means that the growth of lithium dendrites has pressed the separator. If the battery continues to operate, the separator has a great risk of being punctured. Therefore, a safety hazard alarm should be issued at this time. To ensure safety, the battery It should be stopped for repair or replacement. The greater the voltage signal detected by the early warning system in the embodiment of the present application, the greater the compressive stress of lithium dendrites on the piezoelectric sensing layer.
  • the second aspect of the embodiment of the present application provides an online monitoring system for lithium dendrites of secondary battery electrodes, including: a battery unit, a piezoelectric sensing unit and an early warning detection unit, and the piezoelectric sensing unit is arranged between the electrode sheet and the diaphragm of the battery unit , and the piezoelectric sensing unit is electrically connected to the early warning detection unit.
  • the secondary battery electrode lithium dendrite online monitoring system provided in the second aspect of the embodiment of the present application, the battery unit, the early warning detection unit, and the piezoelectric sensing unit arranged between the electrode sheet and the diaphragm of the battery unit, the piezoelectric sensing unit and The early warning detection unit is electrically connected.
  • the piezoelectric sensing unit is subjected to the physical pressure generated by the growth of lithium dendrites, a voltage signal will be generated; and the generated voltage signal will be transmitted to the early warning monitoring unit.
  • the change of the voltage signal of the piezoelectric sensing unit is monitored in real time through the early warning detection unit, so as to monitor the growth of lithium dendrites in the battery unit in real time.
  • the early warning monitoring unit sends early warning information in time to ensure the safety performance of the battery unit.
  • the piezoelectric sensing unit includes: at least one of a lithium niobate sensing unit, a lithium tantalate sensing unit, a barium titanate sensing unit, and a lead titanate sensing unit. These material sensing units have good piezoelectricity. Electrical properties, high sensitivity, when the sensing unit of these materials is subjected to the physical pressure of lithium dendrites, the electric polarization phenomenon will occur inside the material due to the force, which will cause the surface of the medium to be charged, and then generate a gas voltage signal.
  • the thickness of the piezoelectric sensing unit is 10-15 ⁇ m; this thickness can take into account both ion migration shuttle and piezoelectric sensing effect. If the piezoelectric sensing unit is too thin, it is not conducive to the timely preparation of the physical stress generated by the induction of lithium dendrite growth; if the piezoelectric sensing unit is too thick, it will reduce the efficiency of ion migration and shuttling to a certain extent, and the too thick piezoelectric sensing Cells also reduce the energy density of the battery. In some specific embodiments, the thickness of the piezoelectric sensing unit may be 10-11 ⁇ m, 11-13 ⁇ m, 13-15 ⁇ m and so on.
  • the range detection range of the voltage signal by the early warning detection unit is 50 ⁇ 500 pC/N.
  • the early warning detection unit in the embodiment of the present application has a wide detection range for voltage signals, and can efficiently and sensitively detect changes in electrical signals of the piezoelectric sensing unit.
  • the secondary battery electrode lithium dendrite on-line monitoring system also includes an inert film unit, which is arranged between the piezoelectric sensing unit and the electrode sheet of the battery unit, and can isolate the electrolyte from the piezoelectric sensing unit. The chemical reaction between them has good ion migration and transport performance, and will not affect the battery operation.
  • the inert film unit material includes: at least one of silicon oxide, lithium carbonate, lithium aluminum germanium phosphate, and lithium titanium aluminum phosphate, all of which can block the chemical reaction between the electrolyte and the piezoelectric sensing layer , but also has high ion mobility.
  • the thickness of the inert film unit is 3-8 ⁇ m; this thickness can effectively isolate the contact reaction between the electrolyte and the piezoelectric sensing unit, and prevent the excessive thickness of the inert film unit from reducing the energy density of the battery.
  • the third aspect of the embodiment of the present application provides a secondary battery, the secondary battery includes a piezoelectric sensing layer disposed between the electrode sheet and the diaphragm, and the piezoelectric sensing layer is electrically connected to the early warning detection system.
  • the piezoelectric induction layer is provided between the electrode sheet and the diaphragm, and the piezoelectric induction layer is electrically connected to the early warning detection system, during the operation of the battery, the piezoelectric The sensing layer can monitor the growth of lithium dendrites in the battery in real time, thereby monitoring the safety status of the battery in real time. Therefore, the secondary battery provided by the embodiment of the present application has high safety, good controllability, and broad application prospects.
  • the piezoelectric sensing layer is disposed between the negative electrode sheet and the separator.
  • the ion reduction reaction mainly occurs at the negative electrode of the battery.
  • lithium ions are reduced at the negative electrode, it is easier to form a dendritic metal lithium element, that is, lithium dendrites. Therefore, the risk of lithium dendrite formation on the surface of the negative electrode is greater, and it is more conducive to testing the safety performance of the battery system if the piezoelectric sensing layer is arranged between the negative electrode and the separator.
  • the negative electrode sheet of the secondary battery is selected from one with lower potential such as lithium metal negative electrode, sodium metal negative electrode, and graphite negative electrode.
  • the positive electrode sheet material of the secondary battery is selected from one or more of ternary transition metal oxides, sulfides, lithium iron phosphate, and the like.
  • the separator of the secondary battery may be a PP film and a PE film.
  • the electrolyte of the secondary battery may be liquid LiPF 6 /EC, LiPF 6 /EC:DMC, and the like.
  • the material of the piezoelectric sensing layer includes: at least one piezoelectric sensing material selected from lithium niobate, lithium tantalate, barium titanate, and lead titanate.
  • the thickness of the piezoelectric sensing layer is 10-15 ⁇ m.
  • an inert film layer is further provided between the piezoelectric sensing layer and the electrode sheet, and the inert film layer has ion migration properties.
  • a lithium ion battery electrode lithium dendrite online monitoring method comprising steps:
  • the positive electrode is nickel-cobalt-manganese 532 ternary positive electrode
  • the negative electrode is graphite
  • the separator is 15 ⁇ m PE film
  • the separator is coated with a 10 ⁇ m thick lithium niobate film
  • the electrolyte is LiPF 6 /EC.
  • the lithium niobate thin film leads a wire to connect the piezoelectric sensor in the early warning detection system, and the measurement range is 50 ⁇ 500 pC/N.
  • a lithium ion battery electrode lithium dendrite online monitoring method comprising steps:
  • the positive electrode is nickel-cobalt-manganese 532 ternary positive electrode
  • the negative electrode is graphite
  • the separator is 15 ⁇ m PE film
  • the lithium niobate film is deposited on inert silicon dioxide
  • the electrolyte is LiPF 6 /EC.
  • the lithium niobate thin film leads a wire to connect the piezoelectric sensor in the early warning detection system, and the measurement range is 50 ⁇ 500 pC/N.
  • the positive electrode uses nickel-cobalt-manganese 532 ternary positive electrode, the negative electrode is graphite, and the electrolyte is LiPF 6 /EC.
  • the lithium metal sheet is wrapped on the wire and pressed, put in a separator bag and placed between the positive electrode and the negative electrode, as a participating battery , to prepare a three-electrode battery.
  • the negative electrode potential and battery voltage are monitored in real time through the battery management system.
  • a lithium analysis alarm is issued in time, and the battery stops working.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Secondary Cells (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本申请属于电池技术领域，尤其涉及一种二次电池电极锂枝晶在线监测方法及系统，以及一种二次电池。其中，二次电池电极锂枝晶在线监测方法，包括步骤：在二次电池的电极片与隔膜之间设置压电感应层；将所述压电感应层与预警检测系统电连接；在电池运行过程中，所述预警检测系统实时监测电池中所述压电感应层产生的电压信号；通过所述电压信号判断锂枝晶的生长情况，获得所述二次电池的安全状况。本申请通过在电池隔膜与电极片之间设置压电感应层，通过对压电感应层应力的检测，可以直接实时在线监测预警电池的安全状况，而无需前期模拟环境测试，也无需拆解电池进行检测，在线监测方法操作灵活方便，且检测准确性高，成本低，易规模化应用。

Description

二次电池电极锂枝晶在线监测方法及系统、二次电池 技术领域
本申请属于电池技术领域，尤其涉及一种二次电池电极锂枝晶在线监测方法及系统，以及一种二次电池。
 背景技术
锂离子二次电池凭借高能量密度、优良的循环性能、环境友好等众多优点，现已广泛运用于各种便携式电子设备、电器和新能源汽车等领域。广泛的运用对电池的各项性能有了更高的要求，尤其是安全性能问题。作为锂离子二次电池安全隐患之一的锂枝晶，是锂负极在充放电循环的过程中、锂离子在负极表面不均匀沉积形成的沉积物。在电池使用时，锂枝晶会不断形成、生长或者断裂。断裂的枝晶失去活性不再贡献电池容量；而不断生长的锂枝晶会刺穿隔膜从而引起电池短路，形成热失控，严重时会引发电池起火、爆炸等威胁使用者人身安全的问题。目前，针对锂离子电池的安全问题设计的预警防护系统多是基于超声或X射线的热传感器、烟雾传感器或红外传感器等。其中，在线监测的技术方案无论是超声还是内阻测试都存在一定弊端。对于检测仪器的要求、测试环境和成本都比较高，难以大规模商业化应用。而通过测试内阻或拆解电池检查则需要停机检测，在使用过程中多有不便。因此，在线监测预警系统的开发是非常有必要的。
 技术问题
现有技术中，针对锂枝晶的在线监测方法及系统有：通过前期应用三电极测试系统检测测试工况下电池的析锂情况，通过负极电位准确标记测试工况下析锂的开始容量位置和持续容量，并与锂离子电池的端电压相对应。在实际应用时，只需检测实际工况下的端电压，并通过系统转换成负极电位，实时检测锂离子电池的析锂状况从而监测锂枝晶的生成。但是该方法局限性在于：（1）前期需要根据实际应用状况设计测试项目进行测试；（2）实际应用情况和测试环境可能存在差异。
 技术解决方案
本申请的目的在于提供一种二次电池电极锂枝晶在线监测方法及系统，以及一种二次电池，旨在一定程度上解决现有二次电池中电极锂枝晶的生成难以在线及时准确检测的问题。
为实现上述申请目的，本申请采用的技术方案如下：
第一方面，本申请提供一种二次电池电极锂枝晶在线监测方法，包括以下步骤：
在二次电池的电极片与隔膜之间设置压电感应层；将所述压电感应层与预警检测系统电连接；
在电池运行过程中，所述预警检测系统实时监测电池中所述压电感应层产生的电压信号；
通过所述电压信号判断锂枝晶的生长情况，获得所述二次电池的安全状况。
进一步地，所述压电感应层的材料包括：铌酸锂、钽酸锂、钛酸钡、钛酸铅中的至少一种压电感应材料。
进一步地，所述压电感应层的厚度为10~15μm。
进一步地，所述在二次电池的电极片与隔膜之间设置压电感应层的步骤包括：采用脉冲激光沉积方法制备所述压电感应层；将所述压电感应层贴合设置在所述隔膜表面。
进一步地，当所述预警检测系统检测到电压信号范围为150 ~400 pC/N时，发出安全隐患警报，电池停止运行。
进一步地，在所述压电感应层与所述电极片之间还设置有惰性薄膜层，所述惰性薄膜层具有离子迁移性能。
进一步地，所述惰性薄膜层的厚度为3~8μm。
进一步地，所述惰性薄膜层的材料包括：氧化硅、碳酸锂、磷酸锗铝锂、磷酸钛铝锂中的至少一种。
进一步地，所述电极片选自负极片。
第二方面，本申请提供一种二次电池电极锂枝晶在线监测系统，所述二次电池电极锂枝晶在线监测系统包括：电池单元、压电感应单元和预警检测单元，所述压电感应单元设置在所述电池单元的电极片与隔膜之间，且所述压电感应单元与所述预警检测单元电连接。
进一步地，所述压电感应单元包括：铌酸锂感应单元、钽酸锂感应单元、钛酸钡感应单元、钛酸铅感应单元中的至少一种。
进一步地，所述压电感应单元的厚度为10~15μm。
进一步地，所述预警检测单元对电压信号的范围检测范围为50~500 pC/N。
第三方面，本申请提供一种二次电池，所述二次电池包括设置在电极片和隔膜之间的压电感应层，所述压电感应层与预警检测系统电连接。
 有益效果
本申请第一方面提供的二次电池电极锂枝晶在线监测方法，在电极片与隔膜之间设置压电感应层，且压电感应层与预警检测系统电连接，在电池循环充放电的运行过程中，当压电感应层受到锂枝晶生长产生的物理压力时，压电感应层内部会产生电极化现象，引起介质表面带电，进而产生电压信号。预警监测系统可以实时监测电池中的压电感应层产生的电压信号，当检测到电压信号时则说明锂枝晶已生长到隔膜，会有刺穿隔膜的风险，此时电池短路风险较高。因此，通过预警监测系统实时监测电压信号的强弱，即可实时在线判断电池中锂枝晶的生长情况，从而获得二次电池安全状况。本申请通过在电池隔膜与电极片之间设置压电感应层，当锂枝晶生长到一定程度并触及压电感应层时，通过对压电感应层产生的应力作用，释放电信号，经电路传输至预警检测系统，可以直接实时在线监测预警电池的安全状况，而无需前期模拟环境测试，也无需拆解电池进行检测，在线监测方法操作灵活方便，且检测准确性高，成本低，易规模化应用。
本申请第二方面提供的二次电池电极锂枝晶在线监测系统，电池单元、预警检测单元和设置在所述电池单元的电极片与隔膜之间的压电感应单元，该压电感应单元与所述预警检测单元电连接。在电池循环充放电的运行过程中，压电感应单元受到锂枝晶生长产生的物理压力时，会产生电压信号；而产生的电压信号会传递到预警监测单元。通过预警检测单元实时监测压电感应单元电压信号的变化，从而实时监测电池单元中锂枝晶的生长情况，当电压信号增大时，说明此时锂枝晶对压电感应层产气的应力较大，锂枝晶有刺穿隔膜的风险，预警监测单元及时发出预警信息，确保电池单元的安全性能。
本申请第三方面提供的二次电池，由于在电极片和隔膜之间设置有压电感应层，且压电感应层与预警检测系统电连接，因而在电池运行过程中，通过压电感应层可实时监测电池内锂枝晶的生长情况，从而实时监测电池的安全状况。因此，本申请提供的二次电池安全性高，可控性能好，应用前景广。
 附图说明
为了更清楚地说明本申请实施例中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本申请实施例1提供的二次电池电极锂枝晶在线监测系统结构示意图；
图2是本申请实施例2提供的二次电池电极锂枝晶在线监测系统结构示意图。
 本发明的实施方式
为了使本申请要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本申请进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本申请，并不用于限定本申请。
本申请中，术语“和/或”，描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B的情况。其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。
本申请中，“至少一个”是指一个或者多个，“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达，是指的这些项中的任意组合，包括单项（个）或复数项（个）的任意组合。例如，“a，b或c中的至少一项（个）”，或，“a，b和c中的至少一项（个）”，均可以表示：a，b，c，a-b（即a和b），a-c，b-c，或a-b-c，其中a，b，c分别可以是单个，也可以是多个。
应理解，在本申请的各种实施例中，上述各过程的序号的大小并不意味着执行顺序的先后，部分或全部步骤可以并行执行或先后执行，各过程的执行顺序应以其功能和内在逻辑确定，而不应对本申请实施例的实施过程构成任何限定。
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。
本申请实施例说明书中所提到的相关成分的重量不仅仅可以指代各组分的具体含量，也可以表示各组分间重量的比例关系，因此，只要是按照本申请实施例说明书相关组分的含量按比例放大或缩小均在本申请实施例说明书公开的范围之内。具体地，本申请实施例说明书中的质量可以是µg、mg、g、kg等化工领域公知的质量单位。
术语“第一”、“第二”仅用于描述目的，用来将目的如物质彼此区分开，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。例如，在不脱离本申请实施例范围的情况下，第一XX也可以被称为第二XX，类似地，第二XX也可以被称为第一XX。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。
本申请实施例第一方面提供一种二次电池电极锂枝晶在线监测方法，包括以下步骤：
S10. 在二次电池的电极片与隔膜之间设置压电感应层；将压电感应层与预警检测系统电连接；
S20. 在电池运行过程中，预警检测系统实时监测电池中压电感应层产生的电压信号；
S30. 通过电压信号判断锂枝晶的生长情况，获得二次电池的安全状况。
本申请实施例第一方面提供的二次电池电极锂枝晶在线监测方法，在电极片与隔膜之间设置压电感应层，且压电感应层与预警检测系统电连接，在电池循环充放电的运行过程中，当压电感应层受到锂枝晶生长产生的物理压力时，压电感应层内部会产生电极化现象，引起介质表面带电，进而产生电压信号。预警监测系统可以实时监测电池中的压电感应层产生的电压信号，当检测到电压信号时则说明锂枝晶已生长到隔膜，会有刺穿隔膜的风险，此时电池短路风险较高。因此，通过预警监测系统实时监测电压信号的强弱，即可实时在线判断电池中锂枝晶的生长情况，从而获得二次电池安全状况。本申请实施例通过在电池隔膜与电极片之间设置压电感应层，当锂枝晶生长到一定程度并触及压电感应层时，通过对压电感应层产生的应力作用，释放电信号，经电路传输至预警检测系统，可以直接实时在线监测预警电池的安全状况，而无需前期模拟环境测试，也无需拆解电池进行检测，在线监测方法操作灵活方便，且检测准确性高，成本低，易规模化应用。
在一些实施例中，上述步骤S10中，在二次电池的电极片与隔膜之间设置压电感应层的步骤包括：
S11. 采用脉冲激光沉积方法制备压电感应层；有利于形成膜层稳定、致密、均匀、平整度好的压电感应层，从而有利于压电感应层对锂枝晶生长产生的物理压力更准确快捷进行感应。
S12. 将压电感应层贴合设置在隔膜表面。通过将压电感应层与隔膜贴合设置，使压电感应层能更及时准确的感受锂枝晶生长对隔膜产生的应力，从而提高检测灵敏度和准确性。
在一些实施例中，压电感应层的材料包括：铌酸锂、钽酸锂、钛酸钡、钛酸铅中的至少一种压电感应材料；这些材料具有良好的压电性质，灵敏度高，当对这些压电材料施加物理压力时，材料因受力内部产生电极化现象，引起介质表面带电，进而产气电压信号。同时，这些材料也具有较好的离子迁移传输性能，对电池的电化学性能影响小。本申请实施例压电感应层中采用的这些压电感应材料对物理压力的感受明敏度足以保证预警检测的及时性和准确性，压电感应层受到的锂枝晶的压迫应力越大，电压信号越大。在一些优选实施例中，压电感应层采用铌酸锂层，铌酸锂具有良好的压电性质，约为6×10 -12库伦/公斤厘米平方，且灵敏度高。
在一些实施例中，压电感应层的厚度为10~15μm，该厚度能兼顾离子迁移穿梭和压电感应效果。若压电感应层太薄，则不利于及时准备的感应锂枝晶生长产生的物理应力；若压电感应层太厚，则会一定程度上降低离子迁移穿梭效率，且过厚的压电感应层也会降低电池的能量密度。在一些具体实施例中，压电感应层的厚度可以是10~11μm、11~13μm、13~15μm等。
在一些实施例中，在压电感应层与电极片之间还设置有惰性薄膜层，惰性薄膜层具有离子迁移性能。本申请实施例在压电感应层与电极片之间设置的惰性薄膜层，既能够隔绝电解液与压电感应层之间的化学反应，又具有较好的离子迁移传输性能，不会影响电池运行。
在一些实施例中，惰性薄膜层的材料包括：氧化硅、碳酸锂、磷酸锗铝锂、磷酸钛铝锂中的至少一种，这些材料均可以阻挡电解液与压电感应层之间的化学反应，而且也具有较高的离子迁移传输性。在一些优选实施例中，惰性薄膜层采用氧化硅层，氧化硅形成的惰性薄膜层，不但膜层物理和化学稳定性好，可有效阻挡电解液与压电感应层中材料反应，而且形成的膜层具有丰富的微孔，离子能够高效的迁移传输。
在一些实施例中，惰性薄膜层的厚度为3~8μm；该厚度即可以有效隔绝电解液与压电感应层接触反应，又避免膜层过厚降低电池能量密度。在一些具体实施例中，惰性薄膜层的厚度可以是3~5μm、5~6μm、6~8μm等。
在一些实施例中，电极片选自负极片。离子还原反应主要发生在电池负极，当锂离子在负极还原时更容易形成的树枝状金属锂单质，即锂枝晶。因此，负极片表面形成锂枝晶的风险更大，将压电感应层设置在负极片与隔膜之间的更有利于检测电池体系的安全性能。
在一些实施例中，压电感应层通过导电线路与预警检测系统电连接，通过导电线路将压力信号传递到预警检测系统实时监测电池内锂枝晶的生长情况。
在一些实施例中，上述步骤S20中，在电池运行过程中，预警检测系统实时监测电池中压电感应层产生的电压信号。本申请实施例预警检测系统可通过实施监测压电感应层电压信号的变化，达到实时检测电池内锂枝晶生长情况，从而判断电池的安全状况。
在一些实施例中，上述步骤S30中，通过电压信号判断锂枝晶的生长情况，即可获得二次电池的安全状况。在一些实施例中，当预警检测系统检测到电压信号范围为150 ~400 pC/N时，说明锂枝晶的生长已经压迫到隔膜了，若电池继续运行则隔膜有很大的被刺破的风险，因此，此时应该发出安全隐患警报，为确保安全，电池应该停止运行，进行检修或更换。本申请实施例预警系统检测到的电压信号越大，则说明压电感应层受到的锂枝晶的压迫应力越大。
本申请实施例第二方面提供一种二次电池电极锂枝晶在线监测系统，包括：电池单元、压电感应单元和预警检测单元，压电感应单元设置在电池单元的电极片与隔膜之间，且压电感应单元与预警检测单元电连接。
本申请实施例第二方面提供的二次电池电极锂枝晶在线监测系统，电池单元、预警检测单元和设置在电池单元的电极片与隔膜之间的压电感应单元，该压电感应单元与预警检测单元电连接。在电池循环充放电的运行过程中，压电感应单元受到锂枝晶生长产生的物理压力时，会产生电压信号；而产生的电压信号会传递到预警监测单元。通过预警检测单元实时监测压电感应单元电压信号的变化，从而实时监测电池单元中锂枝晶的生长情况，当电压信号增大时，说明此时锂枝晶对压电感应层产气的应力较大，锂枝晶有刺穿隔膜的风险，预警监测单元及时发出预警信息，确保电池单元的安全性能。
在一些实施例中，压电感应单元包括：铌酸锂感应单元、钽酸锂感应单元、钛酸钡感应单元、钛酸铅感应单元中的至少一种，这些材料感应单元，具有良好的压电性质，灵敏度高，当对这些材料的感应单元受到锂枝晶的物理压力时，材料因受力内部产生电极化现象，引起介质表面带电，进而产气电压信号。
在一些实施例中，压电感应单元的厚度为10~15μm；该厚度能兼顾离子迁移穿梭和压电感应效果。若压电感应单元太薄，则不利于及时准备的感应锂枝晶生长产生的物理应力；若压电感应单元太厚，则会一定程度上降低离子迁移穿梭效率，且过厚的压电感应单元也会降低电池的能量密度。在一些具体实施例中，压电感应单元的厚度可以是10~11μm、11~13μm、13~15μm等。
在一些实施例中，预警检测单元对电压信号的范围检测范围为50~500 pC/N。本申请实施例预警检测单元对电压信号的检测范围交宽，可高效灵敏的检测压电感应单元电信号的变化。
在一些实施例中，二次电池电极锂枝晶在线监测系统还包括惰性薄膜单元，该单元设置在压电感应单元与电池单元的电极片之间，既能够隔绝电解液与压电感应单元之间的化学反应，又具有较好的离子迁移传输性能，不会影响电池运行。
在一些实施例中，惰性薄膜单元材料包括：氧化硅、碳酸锂、磷酸锗铝锂、磷酸钛铝锂中的至少一种，这些材料均可以阻挡电解液与压电感应层之间的化学反应，而且也具有较高的离子迁移传输性。
在一些实施例中，惰性薄膜单元的厚度为3~8μm；该厚度即可以有效隔绝电解液与压电感应单元接触反应，又避免惰性薄膜单元过厚降低电池能量密度。
本申请实施例第三方面提供一种二次电池，二次电池包括设置在电极片和隔膜之间的压电感应层，压电感应层与预警检测系统电连接。
本申请实施例第三方面提供的二次电池，由于在电极片和隔膜之间设置有压电感应层，且压电感应层与预警检测系统电连接，因而在电池运行过程中，通过压电感应层可实时监测电池内锂枝晶的生长情况，从而实时监测电池的安全状况。因此，本申请实施例提供的二次电池安全性高，可控性能好，应用前景广。
在一些实施例中，压电感应层设置在负极片和隔膜之间。离子还原反应主要发生在电池负极，当锂离子在负极还原时更容易形成的树枝状金属锂单质，即锂枝晶。因此，负极片表面形成锂枝晶的风险更大，将压电感应层设置在负极片与隔膜之间的更有利于检测电池体系的安全性能。
在一些实施例中，二次电池的负极片选自锂金属负极、钠金属负极、石墨负极等电位较低的一种。
在一些实施例中，二次电池的正极片材料选自三元过渡金属氧化物、硫化物、磷酸铁锂等中的一种或多种。
在一些实施例中，二次电池的隔膜可为PP膜以及PE膜。
在一些实施例中，二次电池的电解质可以为液态LiPF 6/EC、LiPF 6/EC：DMC等。
在一些实施例中，压电感应层的材料包括：铌酸锂、钽酸锂、钛酸钡、钛酸铅中的至少一种压电感应材料。
在一些实施例中，压电感应层的厚度为10~15μm。
在一些实施例中，在压电感应层与电极片之间还设置有惰性薄膜层，惰性薄膜层具有离子迁移性能。
本申请上述实施例的有益效果在前文均有详细论述，在此不再赘述。
为使本申请上述实施细节和操作能清楚地被本领域技术人员理解，以及本申请实施例二次电池电极锂枝晶在线监测方法及系统、二次电池的进步性能显著的体现，以下通过多个实施例来举例说明上述技术方案。
实施例1
一种锂离子电池电极锂枝晶在线监测方法，包括步骤：
组装全电池进行测试：正极采用镍钴锰532三元正极，负极为石墨，隔膜为15μm PE膜，隔膜上涂覆厚度为10μm的铌酸锂薄膜，电解液为LiPF 6/EC。铌酸锂薄膜引出一根导线连接预警检测系统中的压电传感器，测量范围为50 ~ 500 pC/N。按附图1结构示意图组装电池，电池组装完成后放置1天，备用。
进行循环测试，记录电池容量变化与循环寿命：在0.5C-1C倍率条件下，经过528周循环充放电后，电池预警检测系统检测到压电信号为183 pC/N，此时停止电池运行。说明本申请实施例能准确监测电池锂枝晶生长情况，从而监控电池安全性能，避免锂枝晶生长刺穿隔膜造成电池安全事故。
实施例2
一种锂离子电池电极锂枝晶在线监测方法，包括步骤：
组装全电池进行测试：正极采用镍钴锰532三元正极，负极为石墨，隔膜为15μm PE膜，10μm的铌酸锂薄膜和8μm惰性二氧化硅层，铌酸锂薄膜沉积在惰性二氧化硅层一侧表面，电解液为LiPF 6/EC。铌酸锂薄膜引出一根导线连接预警检测系统中的压电传感器，测量范围为50 ~ 500 pC/N。按附图2结构示意图组装电池，电池组装完成后放置1天，备用。
进行循环测试，记录电池容量变化与循环寿命：在0.5C-1C倍率条件下，经过528周循环充放电后，电池预警检测系统检测到压电信号为127 pC/N，此时停止电池运行。说明本申请实施例能准确监测电池锂枝晶生长情况，从而监控电池安全性能，避免锂枝晶生长刺穿隔膜造成电池安全事故。
对比例1
以三电极测试系统作为对比例情况，组装全电池进行测试：
正极采用镍钴锰532三元正极，负极为石墨，电解液为LiPF 6/EC，将锂金属薄片包裹在导线上并压制，放入隔膜袋中并置于正极和负极之间，作为参与电池，制备三电极电池。
对三电极电池的正极、负极电位以及电池电压进行工况下的测试和记录；
（1）当电池负极电位小于0 V时，记录此时的时间和SOC；
（2）对电池进行拆解，并对负极进行检测和验证，发现存在析锂，记录锂电位为-0.03~0.02 V，电池电压为3.8~4.02 V，将工况下测试的负极电位值以及对应电池电压值，保存到电池管理系统；
（3）在电池应用中，通过电池管理系统实时监测负极电位和电池电压，当检测到工况下端电压与存入的值接近或一致时，及时发出析锂报警，电池停止工作。
通过比较实施例1~2与对比例1可知：本申请实施例锂离子电池电极锂枝晶在线监测方法，操作灵活方便，且检测准确性高，成本低，易规模化应用。而对比例1采用的三电极检测方法步骤繁琐，需拆解电池验证，可重复性差，检测效率低，不利于规模化应用。
以上所述仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本申请的保护范围之内。

Claims (10)

  1. 一种二次电池电极锂枝晶在线监测方法，其特征在于，包括以下步骤：
    在二次电池的电极片与隔膜之间设置压电感应层；将所述压电感应层与预警检测系统电连接；
    在电池运行过程中，所述预警检测系统实时监测电池中所述压电感应层产生的电压信号；
    通过所述电压信号判断锂枝晶的生长情况，获得所述二次电池的安全状况。
  2. 如权利要求1所述的二次电池电极锂枝晶在线监测方法，其特征在于，所述压电感应层的材料包括：铌酸锂、钽酸锂、钛酸钡、钛酸铅中的至少一种压电感应材料；
    和/或，所述压电感应层的厚度为10~15μm。
  3. 如权利要求1或2所述的二次电池电极锂枝晶在线监测方法，其特征在于，所述在二次电池的电极片与隔膜之间设置压电感应层的步骤包括：采用脉冲激光沉积方法制备所述压电感应层；将所述压电感应层贴合设置在所述隔膜表面。
  4. 如权利要求3所述的二次电池电极锂枝晶在线监测方法，其特征在于，当所述预警检测系统检测到电压信号范围为150 ~400 pC/N时，发出安全隐患警报，电池停止运行。
  5. 如权利要求1或4所述的二次电池电极锂枝晶在线监测方法，其特征在于，在所述压电感应层与所述电极片之间还设置有惰性薄膜层，所述惰性薄膜层具有离子迁移性能。
  6. 如权利要求5所述的二次电池电极锂枝晶在线监测方法，其特征在于，所述惰性薄膜层的厚度为3~8μm；
    和/或，所述惰性薄膜层的材料包括：氧化硅、碳酸锂、磷酸锗铝锂、磷酸钛铝锂中的至少一种。
  7. 如权利要求1或6所述的二次电池电极锂枝晶在线监测方法，其特征在于，所述电极片选自负极片。
  8. 一种二次电池电极锂枝晶在线监测系统，其特征在于，所述二次电池电极锂枝晶在线监测系统包括：电池单元、压电感应单元和预警检测单元，所述压电感应单元设置在所述电池单元的电极片与隔膜之间，且所述压电感应单元与所述预警检测单元电连接。
  9. 如权利要求8所述的二次电池电极锂枝晶在线监测系统，其特征在于，所述压电感应单元包括：铌酸锂感应单元、钽酸锂感应单元、钛酸钡感应单元、钛酸铅感应单元中的至少一种；
    和/或，所述压电感应单元的厚度为10~15μm；
    和/或，所述预警检测单元对电压信号的范围检测范围为50~500 pC/N。
  10. 一种二次电池，其特征在于，所述二次电池包括设置在电极片和隔膜之间的压电感应层，所述压电感应层与预警检测系统电连接。
PCT/CN2021/137619 2021-09-27 2021-12-13 二次电池电极锂枝晶在线监测方法及系统、二次电池 Ceased WO2023045111A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111138907.0 2021-09-27
CN202111138907.0A CN113945627A (zh) 2021-09-27 2021-09-27 二次电池电极锂枝晶在线监测方法及系统、二次电池

Publications (1)

Publication Number Publication Date
WO2023045111A1 true WO2023045111A1 (zh) 2023-03-30

Family

ID=79329436

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/137619 Ceased WO2023045111A1 (zh) 2021-09-27 2021-12-13 二次电池电极锂枝晶在线监测方法及系统、二次电池

Country Status (2)

Country Link
CN (1) CN113945627A (zh)
WO (1) WO2023045111A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118858976A (zh) * 2024-09-25 2024-10-29 南通硬派锂电池有限公司 一种手机锂电池生产用质量检测装置

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118549825B (zh) * 2024-07-30 2024-10-22 中创新航技术研究院(江苏)有限公司 一种锂电池内短路的在线检测方法及其在线检测装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101088183A (zh) * 2004-12-22 2007-12-12 Lg化学株式会社 有机/无机复合微孔膜和由其制造的电化学装置
EP2991135A1 (en) * 2014-08-26 2016-03-02 Lockheed Martin Corporation Methods for dendrite detection and devices for batteries and dendrite sensors
CN105958146A (zh) * 2016-07-27 2016-09-21 芜湖格利特新能源科技有限公司 一种高安全性的光伏微电网储能电池系统
US20190165429A1 (en) * 2017-11-27 2019-05-30 The Regents Of The University Of Michigan Dendrite-Free Lithium Metal Battery by Deformation-Induced Potential Shielding
CN113097648A (zh) * 2021-06-07 2021-07-09 江苏卓高新材料科技有限公司 用于锂金属电池的隔膜及其制备方法
CN113161599A (zh) * 2020-01-07 2021-07-23 荣盛盟固利新能源科技有限公司 电池析锂监测方法及装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013100081A1 (ja) * 2011-12-28 2013-07-04 三菱化学株式会社 非水系電解液及び非水系電解液二次電池
US9384904B2 (en) * 2012-04-06 2016-07-05 Semiconductor Energy Laboratory Co., Ltd. Negative electrode for power storage device, method for forming the same, and power storage device
JP6267482B2 (ja) * 2012-11-02 2018-01-24 株式会社半導体エネルギー研究所 電極の製造方法
EP3051618B1 (en) * 2013-09-26 2018-11-14 Mitsubishi Chemical Corporation Nonaqueous electrolyte solution and nonaqueous electrolyte battery using same
CN106159200B (zh) * 2016-07-29 2019-01-11 中国科学院青岛生物能源与过程研究所 一种具有保护涂层的金属锂负极及其制备和应用
CN111710927A (zh) * 2020-06-29 2020-09-25 香港科技大学 一种金属二次电池的监测预警及维护方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101088183A (zh) * 2004-12-22 2007-12-12 Lg化学株式会社 有机/无机复合微孔膜和由其制造的电化学装置
EP2991135A1 (en) * 2014-08-26 2016-03-02 Lockheed Martin Corporation Methods for dendrite detection and devices for batteries and dendrite sensors
CN105958146A (zh) * 2016-07-27 2016-09-21 芜湖格利特新能源科技有限公司 一种高安全性的光伏微电网储能电池系统
US20190165429A1 (en) * 2017-11-27 2019-05-30 The Regents Of The University Of Michigan Dendrite-Free Lithium Metal Battery by Deformation-Induced Potential Shielding
CN113161599A (zh) * 2020-01-07 2021-07-23 荣盛盟固利新能源科技有限公司 电池析锂监测方法及装置
CN113097648A (zh) * 2021-06-07 2021-07-09 江苏卓高新材料科技有限公司 用于锂金属电池的隔膜及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118858976A (zh) * 2024-09-25 2024-10-29 南通硬派锂电池有限公司 一种手机锂电池生产用质量检测装置

Also Published As

Publication number Publication date
CN113945627A (zh) 2022-01-18

Similar Documents

Publication Publication Date Title
CN106159364B (zh) 方形锂离子电池内部温度的在线监测方法及装置
CN111009679A (zh) 一种三电极电芯、三电极软包电池及其制备方法
CN111766518B (zh) 一种锂离子电池可逆析锂的定量测定方法
CN113078423B (zh) 一种电压-温度耦合测量方法及其装置
WO2023045111A1 (zh) 二次电池电极锂枝晶在线监测方法及系统、二次电池
US12306141B2 (en) Welding defect inspection method
CN108511783A (zh) 一种锂电池
CN108511829A (zh) 一种锂电池
CN116207357A (zh) 三电极电芯结构、三电极电池及负极电位监测方法
CN111129432A (zh) 新型锂离子电池工业用无损检测的参比电极和三电极体系及方法
CN110190325A (zh) 四电极锂硫电池、其制备方法及电极电化学特性监测方法
CN111189884B (zh) 离子传输电阻的测量方法，及极片涂层和隔膜曲折率的测试方法
CN112397789A (zh) 可检测锂枝晶生长三电极电池及方法
CN114019385B (zh) 一种基于单频率阻抗测试的析锂检测方法
CN110715747A (zh) 基于软包电池极耳连接的探测方法
CN102520363A (zh) 一种锂离子电池的低温性能测评方法
US20240361394A1 (en) In-situ ultrasonic method for detecting the state of charge in soft-packaged lithium-ion batteries
CN211017308U (zh) 一种锂离子电池
CN219038234U (zh) 圆柱电芯的膨胀检测装置
CN219037885U (zh) 圆柱电芯膨胀检测装置
CN111830416A (zh) 原位检测锂离子电池硅负极膨胀和失效机制的装置和方法
CN114527172B (zh) 一种电池正极材料稳定性的评估方法
CN115752848A (zh) 电池压力测试装置及使用方法
CN116487676A (zh) 一种单片电池及电池材料的筛选方法
CN115332606A (zh) 一种识别锂枝晶生长位置的锂电池、系统和方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21958222

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21958222

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 23/09/2024)

122 Ep: pct application non-entry in european phase

Ref document number: 21958222

Country of ref document: EP

Kind code of ref document: A1