WO2022266799A1 - Electrochemical device and electronic device - Google Patents

Electrochemical device and electronic device Download PDF

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Publication number
WO2022266799A1
WO2022266799A1 PCT/CN2021/101236 CN2021101236W WO2022266799A1 WO 2022266799 A1 WO2022266799 A1 WO 2022266799A1 CN 2021101236 W CN2021101236 W CN 2021101236W WO 2022266799 A1 WO2022266799 A1 WO 2022266799A1
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WO
WIPO (PCT)
Prior art keywords
negative electrode
electrochemical device
active material
material layer
charge
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PCT/CN2021/101236
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French (fr)
Chinese (zh)
Inventor
刘茜
郑席
杜鹏
谢远森
Original Assignee
宁德新能源科技有限公司
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Application filed by 宁德新能源科技有限公司 filed Critical 宁德新能源科技有限公司
Priority to CN202180005827.XA priority Critical patent/CN114586213A/en
Priority to PCT/CN2021/101236 priority patent/WO2022266799A1/en
Publication of WO2022266799A1 publication Critical patent/WO2022266799A1/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/64Carriers or collectors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the present application relates to the field of electrochemical energy storage, in particular to electrochemical devices and electronic devices.
  • Some embodiments of the present application provide an electrochemical device, the 0.2C discharge capacity of the electrochemical device at -20°C is A, the 0.2C discharge capacity of the electrochemical device at 25°C is B, and 70% ⁇ A/B ⁇ 90%. In some embodiments, 71% ⁇ A/B ⁇ 87%. This shows that the electrochemical device proposed in the examples of the present application has better charge and discharge performance at a low temperature of -20°C, can charge and release more energy, and improves the impact on the charge and discharge performance of the electrochemical device at a low temperature. satisfaction.
  • the 0.2C discharge capacity of the electrochemical device at 45°C is C, 103% ⁇ C/B ⁇ 110%. It shows that the electrochemical device can charge and discharge more energy at medium and high temperature, and has better medium and high temperature charge and discharge performance.
  • the electrochemical device includes a negative electrode, and when the electrochemical device is at a state of charge of 50%, the thickness of the negative electrode is is H 2 , when the electrochemical device is at 0% state of charge, the thickness of the negative electrode is H 1 , and (H 2 -H 1 )/H 1 is 0% to 6%;
  • the electrochemical The device includes a negative electrode. When the electrochemical device is in a state of charge of 100%, the thickness of the negative electrode is H 3 . When the electrochemical device is in a state of charge of 0%, the thickness of the negative electrode is H 1 , (H 3 -H 1 )/H 1 is 0% to 8%.
  • the thickness growth rate of the negative electrode of the electrochemical device when it is charged from 0% state of charge to 50% state of charge.
  • the thickness growth rate of 0% to 6% means that the negative electrode of the electrochemical device in the embodiment of the application is charging
  • the expansion in the process is small, which is beneficial to improve the charge and discharge performance of the electrochemical device.
  • the electrochemical device includes a negative electrode
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer located on the negative electrode current collector
  • the porosity of the negative electrode active material layer is 20% to 50%
  • the negative electrode active material layer The porosity is 35% to 50%. If the porosity of the negative electrode active material layer is less than 20%, it means that the space between the negative electrode materials is small, which may lead to insufficient contact between the negative electrode material and the electrolyte, and then the performance of the negative electrode cannot be fully exerted.
  • the porosity of the negative electrode active material layer is 35% to 50%, and the performance of the electrochemical device is better at this time.
  • the electrochemical device includes a negative electrode, the negative electrode includes a negative electrode current collector and a negative electrode active material layer located on the negative electrode current collector, the negative electrode active material layer includes a negative electrode material, and the negative electrode material includes hard carbon, And satisfy at least one of the following (c) to (g): (c) the bonding force between the negative electrode active material layer and the negative electrode current collector is 10N/m to 50N/m; preferably, the The bonding force between the negative electrode active material layer and the negative electrode current collector is 10N/m to 48N/m; (d) the compacted density of the negative electrode active material layer is 0.9g/ cm3 to 1.25g/cm3 3 ; (e) the particle breakage rate of the negative electrode material is 10% to 40%, optionally, the particle breakage rate of the negative electrode material is 10% to 25%; (f) the X-ray diffraction of the negative electrode material In the spectrum, there is a diffraction peak between 18 ° and 30 °, and the half-he
  • the interlayer spacing of the microchips of the negative electrode material is 0.37nm to 0.39nm. At this time, the dynamic performance of the negative electrode material is better, and the expansion rate of the negative electrode is small.
  • the interlayer spacing of the microchips of the negative electrode material is too small, ions diffuse between the microchip layers. The resistance is relatively large, and the microchip layer is easily stretched by ions, resulting in the overall expansion of the negative electrode.
  • some solvents may be co-embedded, which will destroy the structure of the negative electrode material and affect the overall electrical performance.
  • the electrochemical device satisfies at least one of the following (h) and (i): (h) the 1C discharge capacity of the electrochemical device at 25°C is D, 0.9 ⁇ D/B ⁇ 1; (i) The 5C discharge capacity of the electrochemical device at 25°C is E, 99% ⁇ E/B ⁇ 105%.
  • the three-electrode potential is monitored on the electrochemical device, and the voltage is taken as the ordinate and the state of charge is used as the abscissa.
  • the negative electrode delithiation curve is a slope area from 0.3V to 0.8V, and the negative electrode delithiation curve is The state of charge ratio F below 0.2V is 30% to 80%.
  • the delithiation curve of the negative electrode is a slope area from 0.3V to 0.8V (the slope area refers to the angle between the electrochemical curve and the 0V horizontal line is greater than 30°, that is, compared with the initial curve, it is an obvious upward trend), and the delithiation curve of the negative electrode is at 0.2V
  • the following state of charge ratio F is 30% to 80%.
  • the slope area is an intrinsic characteristic of the hard carbon material, and the state of charge ratio F of the delithiation curve of different negative electrode materials is different below 0.2V.
  • the kinetic performance of the electrochemical device is better when the proportion F is 30% to 80%, but if the charge state proportion F of the negative electrode delithiation curve is below 0.2V is greater than 80%, the overall voltage of the electrochemical device is low, Energy density is reduced.
  • the electrochemical device includes a positive electrode and a negative electrode
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer on the positive electrode fluid
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector.
  • the weight of the single-sided positive electrode active material layer is M 1
  • the weight of the single-sided negative electrode active material layer per unit area is M 2
  • M 1 /M 2 is 2 to 6.
  • the CB value of the electrochemical device is 0.9 to 1.1, optionally, the CB value is 0.95 to 1.06; wherein, the CB value is the ratio of the negative electrode capacity to the positive electrode capacity under the same area.
  • CB negative electrode capacity/positive electrode capacity
  • the negative electrode capacity CW negative electrode ⁇ gram capacity negative electrode ⁇ active material percentage content negative electrode
  • the positive electrode capacity CW positive electrode ⁇ gram capacity positive electrode ⁇ active material percentage content positive electrode
  • the percentage of active material in the positive electrode and the percentage of active material in the negative electrode respectively represent the mass ratio of the positive electrode material to the positive electrode active material layer and the mass ratio of the negative electrode material to the negative electrode active material layer.
  • the electrochemical device is a lithium-ion battery
  • the CB value when the CB value is too small, it may cause the positive electrode to provide Too many lithium ions in the negative electrode will cause lithium precipitation, and when the CB value is too large, it may lead to a decrease in energy density.
  • the present application also proposes an electronic device, including any one of the above electrochemical devices.
  • the 0.2C discharge capacity of the electrochemical device at -20°C is A
  • the 0.2C discharge capacity of the electrochemical device at 25°C is B
  • the electrochemical device proposed in the examples of the present application has better low-temperature charge and discharge performance at a low temperature of -20° C., and can charge and release more energy.
  • Electrochemical devices such as lithium-ion batteries, are widely used in various fields and have a wide range of usage scenarios. At low temperatures, the charge-discharge performance of electrochemical devices is often unsatisfactory, and further improvements are expected.
  • 100% state of charge refers to the state where the electrochemical device is charged to the maximum design voltage with a constant current, and includes the state after standing (generally standing for 10 minutes), which is regarded as Fully charged state, unless otherwise specified, the maximum design voltage includes but not limited to 4.48V, 4.5V, 4.53V or 4.45V, or even higher voltage.
  • 0% state of charge refers to the state of constant current discharge of the electrochemical device to the minimum design voltage, and includes the state after standing (generally standing for 10 minutes), which is considered to be fully charged.
  • the maximum design voltage includes but is not limited to 3.0V, 2.8V, 2.6V or 2.0V, or even lower voltage.
  • the 50% state of charge includes the state after standing (generally standing for 10 minutes).
  • Some embodiments of the present application provide an electrochemical device, the 0.2C discharge capacity of the electrochemical device at -20°C is A, the 0.2C discharge capacity of the electrochemical device at 25°C is B, and 70% ⁇ A/B ⁇ 90%.
  • the discharge capacity B of the electrochemical device at 0.2C at 25°C characterizes the charge and discharge performance of the electrochemical device at room temperature
  • the discharge capacity A of the electrochemical device at 0.2C at -20°C characterizes the electrochemical device
  • the charge and discharge performance of the device at low temperature, A/B characterizes the retention rate of the charge and discharge performance of the electrochemical device at low temperature, because 70% ⁇ A/B ⁇ 90%, this shows that the electrochemical device proposed in the examples of this application
  • the device has better charge and discharge performance at a low temperature of -20°C, can charge and release more energy, and improves the satisfaction with the charge and discharge performance of the electrochemical device at low temperature.
  • the 0.2C discharge capacity of the electrochemical device at 45°C is C, 103% ⁇ C/B ⁇ 110%. In some embodiments, the 0.2C discharge capacity of the electrochemical device at 45°C is C, which characterizes the charge and discharge performance of the electrochemical device at medium and high temperatures, and 103% ⁇ C/B ⁇ 110% indicates that the electrochemical device can be used in medium and high temperature. Charge and release more energy at high temperature, and have better medium and high temperature charge and discharge performance.
  • the electrochemical device includes a negative electrode
  • the thickness of the negative electrode is H2 when the electrochemical device is at a state of charge of 50%
  • the thickness of the negative electrode is H1 when the electrochemical device is at a state of charge of 0%
  • ( H 2 -H 1 )/H 1 is 0% to 6%.
  • (H 2 -H 1 )/H 1 represents the thickness growth rate of the negative electrode of the electrochemical device when it is charged from 0% state of charge to 50% state of charge
  • the thickness growth rate is 0% to 6 % indicates that the expansion of the negative electrode of the electrochemical device in the embodiment of the present application is small during the charging process, which is conducive to improving the charge and discharge performance of the electrochemical device.
  • the electrochemical device includes a negative electrode
  • the thickness of the negative electrode is H 3 when the electrochemical device is in a 100% state of charge
  • the thickness of the negative electrode is H 1 when the electrochemical device is in a 0% state of charge
  • ( H 3 -H 1 )/H 1 is 0% to 8%.
  • (H 3 -H 1 )/H 1 represents the thickness growth rate of the negative electrode of the electrochemical device when it is charged from 0% state of charge to 100% state of charge
  • the thickness growth rate is 0% to 8 % means that the expansion of the negative electrode of the electrochemical device in the embodiment of the present application is small during the whole charging process, which is beneficial to improve the charge and discharge performance of the electrochemical device.
  • the electrochemical device includes a negative electrode
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer located on the negative electrode current collector
  • the porosity of the negative electrode active material layer is 20% to 50%.
  • the porosity of the negative electrode active material layer is less than 20%, it means that the space between the negative electrode materials is small, which may lead to insufficient contact between the negative electrode material and the electrolyte, and then cause the performance of the negative electrode to not be fully utilized.
  • the porosity of the active material layer exceeds 50%, the gap between the particles of the negative electrode material may be too large, resulting in poor electrical contact between the particles of the negative electrode material, which affects the performance of the electrochemical device.
  • the porosity of the negative electrode active material layer is 35% to 50%, and the performance of the electrochemical device is better at this time.
  • the electrochemical device includes a negative electrode, the negative electrode includes a negative electrode current collector and a negative electrode active material layer located on the negative electrode current collector, the negative electrode active material layer includes a negative electrode material, the negative electrode material includes hard carbon, the negative electrode active material layer and
  • the binding force between negative electrode current collectors is 10 N/m to 50 N/m. In some embodiments, if the bonding force between the negative electrode active material layer and the negative electrode current collector is too small, it may cause peeling off or poor contact between the negative electrode active material layer and the negative electrode current collector during the charging and discharging process of the electrochemical device, It is not conducive to electron conduction and affects test performance. If the binding force between the negative electrode active material layer and the negative electrode current collector is too large, it may be necessary to use too much binder, which may be detrimental to the conductivity of the negative electrode and affect the kinetic performance.
  • the brand of the instrument used for testing the adhesion between the negative electrode active material layer and the negative electrode current collector is Instron, the model is 33652, take the negative electrode (width 30mm ⁇ length (100mm to 160mm)), and use double-sided adhesive tape (model: 3M9448A, width 20mm) ⁇ Length (90mm to 150mm)) is fixed on the steel plate, fix the paper tape with the same width as the negative electrode and the negative electrode side with adhesive tape, adjust the limit block of the tension machine to a suitable position, fold the paper tape upwards and slide 40mm , the slip rate is 50mm/min, and the adhesion force between the negative electrode active material layer and the negative electrode current collector is tested under 180° (that is, stretched in the opposite direction).
  • the compacted density of the negative electrode active material layer is 0.9 g/cm 3 to 1.25 g/cm 3 . Test of the compacted density of the negative electrode active material layer:
  • T0 (T1-T2)/2
  • the compaction density of the negative electrode active material layer if the compaction density of the negative electrode active material layer is too small, it will be unfavorable to the volumetric energy density of the electrochemical device, and it will also be unfavorable to the conduction of electrons in the negative electrode active material layer. If the compaction density of the negative electrode active material layer is too large, the electrolyte may not be able to fully infiltrate the negative electrode active material layer, which is not conducive to fully exerting the performance of the negative electrode.
  • the particle crushing rate of the negative electrode material is 10% to 40%. In some embodiments, the particle crushing rate of the negative electrode material is the ratio of the broken particles of the negative electrode material to the total number of particles of the negative electrode material.
  • a scanning electron microscope SEM
  • the particle breakage rate of the negative electrode material the number of broken particles / the total number of particles, where the broken particles are visible cracks, that is, the gap where the two parts can completely overlap, indicating that the particles are broken , when the total particle number is counted, the particle diameter is larger than 3 ⁇ m, and the particle breakage rate of the negative electrode material in these areas is counted.
  • the negative electrode of the electrochemical device is usually rolled during the manufacturing process, causing the particles of the negative electrode material to be partially broken.
  • a small amount of particle breakage of the negative electrode material is conducive to increasing the contact area with the electrolyte and improving the rate performance. If the rate is too high, the consumption of the electrolyte will be excessively increased.
  • the particle breakage rate of the negative electrode material is 10% to 25%. At this time, the overall performance of the electrochemical device is better.
  • the negative electrode material in the X-ray diffraction pattern of the negative electrode material, there is a diffraction peak between 18° and 30°, and the half-height width of the diffraction peak is 4° to 10°. In some embodiments, there is only one diffraction peak with a full width at half maximum of 4° to 10° between 18° and 30°.
  • the negative electrode material may include hard carbon.
  • the distance between the microchip layers of the negative electrode material is 0.34 nm to 0.4 nm.
  • the negative electrode material includes carbon material, and the distance between the microchip layers is 0.34 nm to 0.4 nm, indicating that the carbon material is amorphous carbon.
  • the microchip layer spacing of the negative electrode material is 0.38nm to 0.39nm. At this time, the dynamic performance of the negative electrode material is better, and the expansion rate of the negative electrode is small.
  • the microchip layer spacing of the negative electrode material is too small, the ions in the microchip The resistance to diffusion between layers is relatively large, and the microchip layer is easily stretched by ions, resulting in the overall expansion of the negative electrode.
  • the interlayer spacing of the microchips is too large, some solvents may be co-embedded, which will destroy the structure of the negative electrode material and affect the overall electrical performance.
  • the 1C discharge capacity of the electrochemical device at 25° C. is D, 0.9 ⁇ D/B ⁇ 1.
  • the charge and discharge performance of the electrochemical device at a rate of 1C is almost the same as that at a rate of 0.2C, and the electrochemical device has good rate performance.
  • the 5C discharge capacity of the electrochemical device at 25° C. is E, 99% ⁇ E/B ⁇ 105%. In some embodiments, when the temperature of the electrochemical device is 25° C., the discharge capacity at 5C rate is greater than the discharge capacity at 0.2C, which indicates that the electrochemical device has good high-rate charge-discharge performance.
  • the three-electrode potential is monitored on the electrochemical device, and the voltage is taken as the ordinate, and the state of charge is used as the abscissa to draw a graph, and the delithiation curve of the negative electrode is a slope area between 0.3V and 0.8V (the slope area refers to the electric The angle between the chemical curve and the 0V horizontal line is greater than 30°, that is, compared with the initial curve, it is an obvious upward trend), and the charge state ratio F of the negative electrode delithiation curve below 0.2V is 30% to 80%.
  • the slope area is an intrinsic characteristic of the hard carbon material, and the state of charge ratio F of the delithiation curve of different negative electrode materials is different below 0.2V.
  • the kinetic performance of the electrochemical device is better when the proportion F is 30% to 80%, but if the charge state proportion F of the negative electrode delithiation curve is below 0.2V is greater than 80%, the overall voltage of the electrochemical device is low, Energy density is reduced.
  • the electrochemical device includes a positive electrode and a negative electrode
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer on the positive electrode fluid
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector.
  • the weight of the single-sided positive electrode active material layer is M 1
  • the weight of the single-sided negative electrode active material layer per unit area is M 2
  • M 1 /M 2 is 2 to 6.
  • one or both sides of the positive electrode current collector can have a positive electrode active material layer
  • M1 is the weight of the positive electrode active material layer per unit area on one side of the positive electrode current collector.
  • one or both sides of the negative electrode current collector have a negative active material layer Material layer
  • M2 is the weight of the negative electrode active material layer per unit area on one side of the negative electrode current collector.
  • the CB value of the electrochemical device is 0.9 to 1.1, optionally, the CB value is 0.95 to 1.06; wherein, the CB value is the ratio of the negative electrode capacity to the positive electrode capacity under the same area.
  • the performance of the positive electrode material and the negative electrode material can be fully utilized without causing waste.
  • the electrochemical device is a lithium-ion battery
  • the CB value is too small, the lithium ions provided by the positive electrode may be too high. If the value is too large, it will cause the negative electrode to precipitate lithium, and when the CB value is too large, it may lead to a decrease in energy density.
  • CB negative electrode capacity/positive electrode capacity
  • the negative electrode capacity is (CW negative electrode ⁇ gram capacity negative electrode ⁇ active material percentage content negative electrode
  • the described positive electrode capacity is (CW positive electrode ⁇ gram capacity positive electrode ⁇ active material percentage content positive electrode )
  • the acquisition of CW and active material percentage The method is to remove the positive and negative electrodes from the battery, punch small discs (such as 1540.25mm2 area) on the flat positive and negative electrodes respectively, and weigh the weight of the active material layer, which is CW (weight of coating film area - empty copper and aluminum foil weight obtained).
  • the small disc is digested with concentrated hydrochloric acid, filtered, dried, and then the percentage of the active material in the active material layer is calculated (the weight of the sample dried after hydrochloric acid digestion/the weight of the sample before hydrochloric acid digestion).
  • Step 2 Gram capacity test: Take the assembled button battery to ensure that the open circuit voltage (OCV) is normal, and each group contains at least 4 parallel samples.
  • the voltage window for the coin cell is set from 0V to 2.5V. Let stand at 25°C for 1 hour, and then discharge the battery with a three-stage low current of 0.05C/50 ⁇ A/20 ⁇ A.
  • the negative electrode realizes SEI (solid electrolyte interfacial film) film formation and records the lithium intercalation capacity (the positive electrode realizes film formation and records lithium intercalation. capacity). Then charge the battery to 2.5V with a current of 0.1C, and record the delithiation capacity of the negative electrode (positive electrode), which is the gram capacity of the negative electrode material (positive electrode material) negative electrode (gram capacity positive electrode ).
  • the negative electrode material includes carbon materials.
  • the preparation process of the negative electrode material is briefly described below to better understand the present application, but this is only exemplary and not intended to limit the present application.
  • Dissolve raw material 1 such as phenolic resin
  • solvent 1 such as ethanol
  • the solvent 1 can also be: water, acetone, methanol, dichloromethane, ethyl acetate, hexane, petroleum ether, toluene or N-methylpyrrolidone.
  • the raw material 1 when the raw material 1 is a soluble material, it may be: epoxy resin, urea-formaldehyde resin, amino resin, ether-based resin, polyester resin, sucrose or glucose.
  • the raw material 1 is an insoluble material, it can directly enter the sintering step.
  • the raw material 1 includes: biomass such as shells, straw, etc., lignocellulose, starch, polyvinyl chloride, polyethylene, polypropylene, polystyrene ABS Plastic etc. It should be understood that this preparation method is only exemplary, and other suitable preparation methods can also be used.
  • the electrochemical device using the negative electrode material proposed in the basic application has excellent low-temperature charge and discharge performance, high rate performance and small expansion rate.
  • a conductive agent and a binder may also be included in the negative electrode active material layer.
  • the conductive agent in the negative electrode active material layer may include at least one of conductive carbon black, Ketjen black, flake graphite, graphene, carbon nanotubes, or carbon fibers.
  • the binder in the negative active material layer may include carboxymethylcellulose (CMC), polyacrylic acid, polyvinylpyrrolidone, polyaniline, polyimide, polyamideimide, polysilicon At least one of oxane, styrene-butadiene rubber, epoxy resin, polyester resin, polyurethane resin or polyfluorene.
  • the mass ratio of the negative electrode material, the conductive agent and the binder in the negative electrode active material layer may be (78 to 98.5):(0.1 to 10):(0.1 to 10).
  • the negative electrode material can be a mixture of silicon-based materials and other materials. It should be understood that the above description is only an example, and any other suitable materials and mass ratios may be used.
  • the negative electrode current collector may use at least one of copper foil, nickel foil, or carbon-based current collector.
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, and the positive electrode active material layer may include a positive electrode material.
  • the positive electrode material includes a positive electrode material capable of absorbing and releasing lithium (Li). Examples of positive electrode materials capable of absorbing/releasing lithium may include lithium cobalt oxide, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium manganate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium iron phosphate, Lithium titanate and lithium-rich manganese-based materials.
  • the chemical formula of lithium cobalt oxide can be as chemical formula 1:
  • M1 means selected from nickel (Ni), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), Copper (Cu), Zinc (Zn), Molybdenum (Mo), Tin (Sn), Calcium (Ca), Strontium (Sr), Tungsten (W), Yttrium (Y), Lanthanum (La), Zirconium (Zr) and At least one of silicon (Si), the values of x, a, b and c are respectively in the following ranges: 0.8 ⁇ x ⁇ 1.2, 0.8 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.2, -0.1 ⁇ c ⁇ 0.2;
  • the chemical formula of lithium nickel cobalt manganate or lithium nickel cobalt aluminate can be as chemical formula 2:
  • M2 means selected from cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), at least one of copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), zirconium (Zr), and silicon (Si),
  • the values of y, d, e and f are respectively in the following ranges: 0.8 ⁇ y ⁇ 1.2, 0.3 ⁇ d ⁇ 0.98, 0.02 ⁇ e ⁇ 0.7, -0.1 ⁇ f ⁇ 0.2;
  • the chemical formula of lithium manganate can be as chemical formula 3:
  • M3 means selected from cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), At least one of copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr) and tungsten (W), the values of z, g and h are respectively in the following ranges Inside: 0.8 ⁇ z ⁇ 1.2, 0 ⁇ g ⁇ 1.0 and -0.2 ⁇ h ⁇ 0.2.
  • the positive active material layer may further include a conductive agent.
  • the conductive agent in the positive active material layer may include at least one of conductive carbon black, Ketjen black, flake graphite, graphene, carbon nanotubes, or carbon fibers.
  • the positive electrode active material layer can also include a binder, and the binder in the positive electrode active material layer can include carboxymethylcellulose (CMC), polyacrylic acid, polyvinylpyrrolidone, polyaniline, polyamide At least one of imine, polyamideimide, polysiloxane, styrene-butadiene rubber, epoxy resin, polyester resin, polyurethane resin or polyfluorene.
  • CMC carboxymethylcellulose
  • the mass ratio of the positive electrode material, the conductive agent and the binder in the positive electrode active material layer may be (80 to 99):(0.1 to 10):(0.1 to 10).
  • the positive active material layer may have a thickness of 10 ⁇ m to 500 ⁇ m. It should be understood that the above description is only an example, and any other suitable material, thickness and mass ratio may be used for the positive electrode active material layer.
  • Al foil may be used as the positive current collector of the positive electrode, and of course, other current collectors commonly used in the art may also be used.
  • the thickness of the positive current collector of the positive electrode may be 1 ⁇ m to 50 ⁇ m.
  • the positive active material layer may be coated only on a partial area of the positive current collector.
  • the electrochemical device includes a separator disposed between the positive electrode and the negative electrode.
  • the isolation film includes at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyethylene terephthalate, polyimide or aramid.
  • polyethylene includes at least one selected from high-density polyethylene, low-density polyethylene, or ultra-high molecular weight polyethylene.
  • the thickness of the isolation film is in the range of about 5 ⁇ m to 50 ⁇ m.
  • the surface of the isolation membrane may also include a porous layer, the porous layer is arranged on at least one surface of the isolation membrane, the porous layer includes inorganic particles and a binder, and the inorganic particles are selected from alumina (Al 2 O 3 ), Silicon oxide (SiO 2 ), magnesium oxide (MgO), titanium oxide (TiO 2 ), hafnium oxide (HfO 2 ), tin oxide (SnO 2 ), cerium oxide (CeO 2 ), nickel oxide (NiO), oxide Zinc (ZnO), calcium oxide (CaO), zirconia (ZrO 2 ), yttrium oxide (Y 2 O 3 ), silicon carbide (SiC), boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide or sulfuric acid at least one of barium.
  • alumina Al 2 O 3
  • Silicon oxide SiO 2
  • magnesium oxide MgO
  • titanium oxide TiO 2
  • hafnium oxide HfO 2
  • the pores of the isolation membrane have a diameter in the range of about 0.01 ⁇ m to 1 ⁇ m.
  • the binder of the porous layer is selected from polyvinylidene fluoride, copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, poly At least one of vinylpyrrolidone, polyvinyl ether, polymethylmethacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
  • the porous layer on the surface of the separator can improve the heat resistance, oxidation resistance and electrolyte wettability of the separator, and enhance the adhesion between the separator and the pole piece.
  • the electrochemical device is wound, stacked or folded.
  • the positive electrode and/or negative electrode of the electrochemical device may be a wound or stacked multi-layer structure, or a single-layer structure in which a single-layer positive electrode, a separator, and a single-layer negative electrode are stacked.
  • the electrochemical device includes a lithium-ion battery, although the present application is not limited thereto.
  • the electrochemical device may also include an electrolyte.
  • the electrolyte may be one or more of a gel electrolyte, a solid electrolyte and an electrolytic solution, and the electrolytic solution includes a lithium salt and a non-aqueous solvent.
  • the lithium salt is selected from LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 , LiSiF 6 , LiBOB or one or more of lithium difluoroborate.
  • LiPF 6 is selected as a lithium salt because it has high ion conductivity and can improve cycle characteristics.
  • the non-aqueous solvent may be a carbonate compound, an ester-based compound, an ether-based compound, a ketone-based compound, an alcohol-based compound, an aprotic solvent, or a combination thereof.
  • the carbonate compound can be a chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate compound or a combination thereof.
  • chain carbonate compounds are diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methyl carbonate Ethyl Ester (MEC) and combinations thereof.
  • chain carbonate compounds are diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methyl carbonate Ethyl Ester (MEC) and combinations thereof.
  • Examples of the cyclic carbonate compound are ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylethylene carbonate (VEC), or combinations thereof.
  • fluorocarbonate compound examples include fluoroethylene carbonate (FEC), 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate, Fluoroethylene carbonate, 1,1,2,2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-carbonic acid - Difluoro-1-methylethylene carbonate, 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate, or a combination thereof.
  • FEC fluoroethylene carbonate
  • 1,2-difluoroethylene carbonate 1,1-difluoroethylene carbonate
  • 1,1,2-trifluoroethylene carbonate Fluoroethylene carbonate, 1,1,2,2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-carbonic acid - Difluoro-1-methylethylene carbonate, 1,1,2-trifluor
  • carboxylate compounds are methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, decanolactone, Valerolactone, mevalonolactone, caprolactone, methyl formate, or combinations thereof.
  • ether compounds are dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxy ethyl ethane, 2-methyltetrahydrofuran, tetrahydrofuran or a combination thereof.
  • organic solvents examples include dimethylsulfoxide, 1,2-dioxolane, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, methyl Amides, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphate esters or combinations thereof.
  • the positive electrode, separator, and negative electrode are sequentially wound or stacked into an electrode part, and then packed into an aluminum-plastic film for packaging, injected with an electrolyte, formed, Encapsulation, that is, made of lithium-ion batteries. Then, performance tests were performed on the prepared lithium-ion batteries.
  • Embodiments of the present application also provide an electronic device including the above electrochemical device.
  • the electronic device in the embodiment of the present application is not particularly limited, and it may be used in any electronic device known in the prior art.
  • electronic devices may include, but are not limited to, notebook computers, pen-based computers, mobile computers, e-book players, cellular phones, portable fax machines, portable copiers, portable printers, headsets, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, cars, motorcycles, power-assisted bicycles, bicycles, Unmanned aerial vehicles, lighting equipment, toys, game consoles, clocks, electric tools, flashlights, cameras, large household storage batteries and lithium-ion capacitors, etc.
  • Preparation of the positive electrode mix lithium cobaltate, conductive carbon black (Super P), and polyvinylidene fluoride (PVDF) according to a weight ratio of 97.5:1.0:1.5, add N-methylpyrrolidone (NMP) as a solvent, and stir evenly .
  • NMP N-methylpyrrolidone
  • the slurry was uniformly coated on the positive electrode current collector aluminum foil with a coating thickness of 80 ⁇ m, and the positive electrode was obtained after drying, cold pressing and cutting.
  • a curing agent m-phenylenediamine
  • epoxy resin: curing agent mass ratio 10:1
  • carry out hydrothermal reaction under the condition of 180°C, wait for the temperature to cool down, and take out the solid part.
  • the negative electrode material, conductive carbon black and styrene-butadiene rubber or modified PAA are dissolved in deionized water at a weight ratio of 96:1.5:2.5 to form negative electrode slurry.
  • Copper foil 6 ⁇ m is used as the current collector of the negative electrode, and the negative electrode slurry is coated on the current collector of the negative electrode.
  • the thickness of the coated negative electrode active material layer is 50 ⁇ m. After drying, it is cooled under the conditions of a pressure of 30 tons and a roll gap of 100 ⁇ m Pressing (rolling) and cutting to obtain the negative electrode, and the porosity of the negative electrode active material layer is 30%.
  • the isolation membrane is polyethylene (PE) with a thickness of 7 ⁇ m.
  • Electrolyte preparation In an environment with a water content of less than 10ppm, LiPF 6 is added to a non-aqueous organic solvent.
  • Preparation of lithium-ion battery stack the positive electrode, separator, and negative electrode in order, so that the separator is in the middle of the positive electrode and the negative electrode to play the role of isolation, and wind up to obtain the electrode assembly.
  • the electrode assembly is placed in the outer packaging aluminum-plastic film, after dehydration at 80°C, the above electrolyte is injected and packaged, and the lithium-ion battery is obtained through chemical formation, degassing, trimming and other processes.
  • the thickness of the copper foil is 6 ⁇ m, which means that the resistance is lower than that of the general copper foil, which is 8 ⁇ m to 16 ⁇ m. Combined with the hard carbon material in this application, it can achieve a large rate of charge and discharge, and has a higher energy density.
  • parameters are changed on the basis of the steps in Example 1, and the specific changed parameters are shown in the table below.
  • Example 1 The difference between Examples 2 to 8 in Table 1 and Example 1 is to adjust the ratio of curing agent to epoxy resin so that the mass ratio of epoxy resin to curing agent (m-phenylenediamine) is 1:1 to 10:1 respectively Between, and, through the control of rolling pressure, so as to realize the interlayer spacing of material microcrystals as shown in Table 1, and obtain a suitable porosity of the negative electrode active material layer.
  • Table 1 shows the respective parameters and evaluation results of Examples 1 to 8 and Comparative Examples 1 to 2.
  • H1 is the thickness of the negative electrode of the electrochemical device at 0% state of charge
  • H2 is the thickness of the negative electrode of the electrochemical device at 50% state of charge
  • H3 is the thickness of the negative electrode of the electrochemical device at 100% state of charge.
  • Example 1 Comparing Example 1 to Example 5 in Table 1, it can be seen that as the distance between the microchip layers of the negative electrode material increases, the A/B value of the electrochemical device increases and the cycle expansion decreases. It can be seen that the microchip layer spacing of the negative electrode material has an impact on the low-temperature charging performance of the electrochemical device. When the microchip layer of the material is small, the performance of the negative electrode material is damaged. The main reason includes the slow ion transport of the electrolyte under low temperature conditions. On this basis, the smaller interlayer spacing of microchips increases the transport resistance of lithium ions, resulting in larger expansion of the negative electrode material.
  • the distance between the microcrystals of the negative electrode should not be greater than 0.4nm, because when the distance between the microchips of the negative electrode material is too large, some solvents in the electrolyte may be co-embedded in the negative electrode material, destroying the structure of the negative electrode material and affecting the overall electrical performance of the electrochemical device.
  • C/B is also relatively sensitive to the lamellar spacing of the material.
  • the intercalation resistance increases due to the low interlayer spacing, the lithium intercalation kinetics of the material is poor, and the structural damage is easy to occur during the lithium intercalation process at high temperature, so it is not good for the material. Bad words.
  • Comparative Example 2 due to the too small interlayer spacing at low temperature, the resulting impedance and polarization are extremely large, resulting in a decrease in low temperature performance.
  • Embodiment 9 to embodiment 12 in table 2 the change of cohesive force is controlled by the change of PAA (polyacrylic acid) adhesive quantity, and the ratio of controlling PAA is 2.8% to 6%, and along with the increase of PAA ratio, active material and The cohesive force between the current collectors increases.
  • the crushing rate of the particles in Examples 13 to 15 is caused by the change of roll pressure during cold pressing, and the roll pressure used is 30 to 50 tons, and the roll pressure used in Comparative Examples 3 to 4 is greater than or equal to 60 tons.
  • Table 2 shows the respective parameters and evaluation results of Example 4 and Examples 9 to 15 and Comparative Examples 3 to 4.
  • the increase of the electronic capacity and the internal resistance of the pole piece affects the kinetic performance of the negative electrode material, thus resulting in a decrease in the capacity retention rate of the electrochemical device at 1C rate and 5C rate.
  • the binding force should not be too small.
  • the negative electrode active material layer and the negative electrode current collector may peel off due to the small binding force, resulting in an increase in internal resistance and a decrease in rate performance.
  • Table 3 shows the respective parameters and evaluation results of Examples 16 to 22.
  • Example 16 to Example 19 adjust and adjust the CB value on the basis of Example 4. It can be seen that as the CB value decreases, the low-temperature capacity retention rate of the electrochemical device and 1C, 5C rate The capacity retention rate has a process of first changing little and then decreasing, and the change of CB from 0.95 to 0.9 decreases the fastest.
  • the negative electrode materials in Examples 16 to 19 belong to hard carbon materials, and hard carbon materials have a certain over-intercalation ability, so when the CB value is 0.95, they can still work normally, thereby obtaining a relatively large energy density, but when the CB value is 0.95
  • the value is lower than 0.95, due to the excessive lithium ions provided by the positive electrode, the negative electrode material will precipitate lithium, and affect the low-temperature performance and rate performance.
  • the CB value exceeds 1.1 the energy density of the electrochemical device will decrease due to the excessive CB value. , and the anode potential rises, forcing the cathode potential to rise, which is not conducive to the performance of electrical performance.

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Abstract

The present application provides an electrochemical device and an electronic device. The discharge capacity of the electrochemical device at 0.2 C at -20°C is A, the discharge capacity of the electrochemical device at 0.2 C at 25°C is B, and 70%≤A/B≤90%. The electrochemical device provided in embodiments of the present application have high low-temperature charge/discharge performance at a low temperature of -20°C.

Description

电化学装置和电子装置Electrochemical devices and electronic devices 技术领域technical field
本申请涉及电化学储能领域,尤其涉及电化学装置和电子装置。The present application relates to the field of electrochemical energy storage, in particular to electrochemical devices and electronic devices.
背景技术Background technique
随着电化学装置(例如,锂离子电池)的发展和进步,对其低温充放电性能提出了越来越高的要求。目前,为了提升电化学装置的低温充放电性能,虽然采取了一些措施得到了一些改进,但还不能令人满意。With the development and progress of electrochemical devices (eg, lithium-ion batteries), higher and higher requirements are placed on their low-temperature charge-discharge performance. At present, in order to improve the low-temperature charge-discharge performance of electrochemical devices, although some measures have been taken and some improvements have been made, they are still not satisfactory.
因此,改善电化学装置的低温充放电性能,仍是亟待解决的问题。Therefore, improving the low-temperature charge-discharge performance of electrochemical devices is still an urgent problem to be solved.
发明内容Contents of the invention
本申请的一些实施例提供了一种电化学装置,电化学装置在-20℃的0.2C放电容量为A,电化学装置在25℃的0.2C放电容量为B,且70%≤A/B≤90%。在一些实施例中,71%≤A/B≤87%。这表明本申请实施例中提出的电化学装置在-20℃的低温下具有较好的充放电性能,能够充入和放出较多的能量,提高对电化学装置的低温下的充放电性能的满意度。Some embodiments of the present application provide an electrochemical device, the 0.2C discharge capacity of the electrochemical device at -20°C is A, the 0.2C discharge capacity of the electrochemical device at 25°C is B, and 70%≤A/B ≤90%. In some embodiments, 71%≤A/B≤87%. This shows that the electrochemical device proposed in the examples of the present application has better charge and discharge performance at a low temperature of -20°C, can charge and release more energy, and improves the impact on the charge and discharge performance of the electrochemical device at a low temperature. satisfaction.
在一些实施例中,电化学装置在45℃的0.2C放电容量为C,103%≤C/B≤110%。表明了电化学装置能够在中高温下充入和放出更多的能量,具有较好的中高温充放电性能。In some embodiments, the 0.2C discharge capacity of the electrochemical device at 45°C is C, 103%≦C/B≦110%. It shows that the electrochemical device can charge and discharge more energy at medium and high temperature, and has better medium and high temperature charge and discharge performance.
在一些实施例中,满足如下(a)或(b)中的至少一者:(a)所述电化学装置包括负极,所述电化学装置在50%荷电状态时,所述负极的厚度为H 2,所述电化学装置在0%荷电状态时,所述负极的厚度为H 1,(H 2-H 1)/H 1为0%至6%;(b)所述电化学装置包括负极,所述电化学装置在100%荷电状态时,所述负极的厚度为H 3,所述电化学装置在0%荷电状态时,所述负极的厚度为H 1,(H 3-H 1)/H 1为0%至8%。表示了电化学装置在从0%荷电状态充电至50%荷电状态时负极的厚度增长率,该厚度增长率为0%至6%表示本申请实施例中的电化学装置的负极在充电过程中的膨胀较小,有利于提高电化学装置的充放电性能。 In some embodiments, at least one of the following (a) or (b) is satisfied: (a) the electrochemical device includes a negative electrode, and when the electrochemical device is at a state of charge of 50%, the thickness of the negative electrode is is H 2 , when the electrochemical device is at 0% state of charge, the thickness of the negative electrode is H 1 , and (H 2 -H 1 )/H 1 is 0% to 6%; (b) the electrochemical The device includes a negative electrode. When the electrochemical device is in a state of charge of 100%, the thickness of the negative electrode is H 3 . When the electrochemical device is in a state of charge of 0%, the thickness of the negative electrode is H 1 , (H 3 -H 1 )/H 1 is 0% to 8%. It represents the thickness growth rate of the negative electrode of the electrochemical device when it is charged from 0% state of charge to 50% state of charge. The thickness growth rate of 0% to 6% means that the negative electrode of the electrochemical device in the embodiment of the application is charging The expansion in the process is small, which is beneficial to improve the charge and discharge performance of the electrochemical device.
在一些实施例中,电化学装置包括负极,负极包括负极集流体和位于负极集流体的负极活性材料层,负极活性材料层的孔隙率为20%至50%,可选的,负极活性材料层的孔隙率为35%至50%。负极活性材料层的孔隙率如果小于20%,说明负极材料之间的空间较小,可能导致负极材料与电解液的接触不充分,进而造成负极的性能无法充分发挥,当负极活性材料层的孔隙率超过50%时,可能因为负极材料的颗粒之间的间隙过大,导致负极材料的颗粒之间电接触不良,影响电化学装置的性能。一些实施例中,负极活性材料层的孔隙率为35%至50%,此时电化学装置的性能更优。In some embodiments, the electrochemical device includes a negative electrode, the negative electrode includes a negative electrode current collector and a negative electrode active material layer located on the negative electrode current collector, the porosity of the negative electrode active material layer is 20% to 50%, and optionally, the negative electrode active material layer The porosity is 35% to 50%. If the porosity of the negative electrode active material layer is less than 20%, it means that the space between the negative electrode materials is small, which may lead to insufficient contact between the negative electrode material and the electrolyte, and then the performance of the negative electrode cannot be fully exerted. When the pores of the negative electrode active material layer When the ratio exceeds 50%, it may be because the gap between the particles of the negative electrode material is too large, resulting in poor electrical contact between the particles of the negative electrode material, which affects the performance of the electrochemical device. In some embodiments, the porosity of the negative electrode active material layer is 35% to 50%, and the performance of the electrochemical device is better at this time.
在一些实施例中,所述电化学装置包括负极,所述负极包括负极集流体和位于所述负极集流体的负极活性材料层,所述负极活性材料层包括负极材料,负极材料包括硬碳,且满足如下(c)至(g)中的至少一者:(c)所述负极活性材料层与所述负极集流体之间的粘结力为10N/m至50N/m;优选的,所述负极活性材料层与所述负极集流体之间的粘结力为10N/m至48N/m;(d)所述负极活性材料层的压实密度为0.9g/cm 3至1.25g/cm 3;(e)所述负极材料的颗粒破碎率为10%至40%,可选的,所述负极材料的颗粒破碎率为10%至25%;(f)所述负极材料的X射线衍射图谱中,在18°至30°之间具有一个衍射峰,所述衍射峰的半高峰宽为4°至10°;(g)所述负极材料的微晶片层间距为0.34nm至0.4nm,可选的,负极材料的微晶片层间距为0.37nm至0.39nm,可选的,负极材料的微晶片层间距为0.37nm至0.38nm。 In some embodiments, the electrochemical device includes a negative electrode, the negative electrode includes a negative electrode current collector and a negative electrode active material layer located on the negative electrode current collector, the negative electrode active material layer includes a negative electrode material, and the negative electrode material includes hard carbon, And satisfy at least one of the following (c) to (g): (c) the bonding force between the negative electrode active material layer and the negative electrode current collector is 10N/m to 50N/m; preferably, the The bonding force between the negative electrode active material layer and the negative electrode current collector is 10N/m to 48N/m; (d) the compacted density of the negative electrode active material layer is 0.9g/ cm3 to 1.25g/cm3 3 ; (e) the particle breakage rate of the negative electrode material is 10% to 40%, optionally, the particle breakage rate of the negative electrode material is 10% to 25%; (f) the X-ray diffraction of the negative electrode material In the spectrum, there is a diffraction peak between 18 ° and 30 °, and the half-height width of the diffraction peak is 4 ° to 10 °; (g) the microchip layer spacing of the negative electrode material is 0.34nm to 0.4nm, Optionally, the interlayer spacing of the microchips of the negative electrode material is 0.37 nm to 0.39 nm, and optionally, the interlayer spacing of the microchips of the negative electrode material is 0.37 nm to 0.38 nm.
负极材料的微晶片层间距为0.37nm至0.39nm,此时负极材料的动力学性能较好,负极膨胀率较小,当负极材料的微晶片层间距过小时,离子在微晶片层之间扩散的阻力较大,微晶片层易于被离子撑开,导致负极整体膨胀。当微晶片层间距过大时,可能存在部分溶剂共嵌入的状况,破坏负极材料结构,影响整体电性能。The interlayer spacing of the microchips of the negative electrode material is 0.37nm to 0.39nm. At this time, the dynamic performance of the negative electrode material is better, and the expansion rate of the negative electrode is small. When the interlayer spacing of the microchips of the negative electrode material is too small, ions diffuse between the microchip layers. The resistance is relatively large, and the microchip layer is easily stretched by ions, resulting in the overall expansion of the negative electrode. When the interlayer spacing of the microchips is too large, some solvents may be co-embedded, which will destroy the structure of the negative electrode material and affect the overall electrical performance.
在一些实施例中,电化学装置满足如下(h)和(i)的至少一项:(h)电化学装置在25℃的1C放电容量为D,0.9<D/B<1;(i)电化学装置在25℃的5C放电容量为E,99%≤E/B≤105%。在一些实施例中,对电化学装置进行三电极电位监控,在以电压为纵坐标,荷电状态为横坐标作图,负极脱锂曲线在0.3V至0.8V为斜坡区,负极脱锂曲线在0.2V以下的荷电状态占比F为30%至80%。负极脱锂曲线在0.3V至0.8V为斜坡区(斜坡区指电化学 曲线与0V水平线夹角大于30°,即相比于初始曲线,为明显的上升趋势),负极脱锂曲线在0.2V以下的荷电状态占比F为30%至80%。在一些实施例中,斜坡区为硬碳材料的本征特性,不同负极材料的脱锂曲线在0.2V以下的荷电状态占比F不同,在负极脱锂曲线在0.2V以下的荷电状态占比F为30%至80%时电化学装置的动力学性能较好,但是若负极脱锂曲线在0.2V以下的荷电状态占比F大于80%时,电化学装置的整体电压低,能量密度降低。In some embodiments, the electrochemical device satisfies at least one of the following (h) and (i): (h) the 1C discharge capacity of the electrochemical device at 25°C is D, 0.9<D/B<1; (i) The 5C discharge capacity of the electrochemical device at 25°C is E, 99%≤E/B≤105%. In some embodiments, the three-electrode potential is monitored on the electrochemical device, and the voltage is taken as the ordinate and the state of charge is used as the abscissa. The negative electrode delithiation curve is a slope area from 0.3V to 0.8V, and the negative electrode delithiation curve is The state of charge ratio F below 0.2V is 30% to 80%. The delithiation curve of the negative electrode is a slope area from 0.3V to 0.8V (the slope area refers to the angle between the electrochemical curve and the 0V horizontal line is greater than 30°, that is, compared with the initial curve, it is an obvious upward trend), and the delithiation curve of the negative electrode is at 0.2V The following state of charge ratio F is 30% to 80%. In some embodiments, the slope area is an intrinsic characteristic of the hard carbon material, and the state of charge ratio F of the delithiation curve of different negative electrode materials is different below 0.2V. The kinetic performance of the electrochemical device is better when the proportion F is 30% to 80%, but if the charge state proportion F of the negative electrode delithiation curve is below 0.2V is greater than 80%, the overall voltage of the electrochemical device is low, Energy density is reduced.
在一些实施例中,电化学装置包括正极和负极,正极包括正极集流体和位于正极流体上的正极活性材料层,负极包括负极集流体和位于负极集流体上的负极活性材料层,单位面积的单面正极活性材料层的重量为M 1,单位面积的单面负极活性材料层的重量为M 2,M 1/M 2为2至6。在一些实施例中,电化学装置的CB值为0.9至1.1,可选的,CB值为0.95至1.06;其中,CB值为相同面积下负极容量与正极容量之间的比值。即,CB=负极容量/正极容量,所述负极容量=CW 负极×克容量 负极×活性材料百分含量 负极,所述正极容量=CW 正极×克容量 正极×活性材料百分含量 正极。活性材料百分含量 正极和活性材料百分含量 负极分别表示正极材料占正极活性材料层的质量比例和负极材料占负极活性材料层的质量比例。通过设置CB值,能够充分发挥正极材料和负极材料的性能,正极材料和合理的匹配负极材料中的硬碳材料,在电化学装置为锂离子电池时,在CB值过小时,可能导致正极提供的锂离子过多,造成负极析锂,在CB值过大时,可能导致能量密度下降。 In some embodiments, the electrochemical device includes a positive electrode and a negative electrode, the positive electrode includes a positive electrode current collector and a positive electrode active material layer on the positive electrode fluid, and the negative electrode includes a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector. The weight of the single-sided positive electrode active material layer is M 1 , the weight of the single-sided negative electrode active material layer per unit area is M 2 , and M 1 /M 2 is 2 to 6. In some embodiments, the CB value of the electrochemical device is 0.9 to 1.1, optionally, the CB value is 0.95 to 1.06; wherein, the CB value is the ratio of the negative electrode capacity to the positive electrode capacity under the same area. That is, CB=negative electrode capacity/positive electrode capacity, the negative electrode capacity=CW negative electrode ×gram capacity negative electrode ×active material percentage content negative electrode , the positive electrode capacity=CW positive electrode ×gram capacity positive electrode ×active material percentage content positive electrode . The percentage of active material in the positive electrode and the percentage of active material in the negative electrode respectively represent the mass ratio of the positive electrode material to the positive electrode active material layer and the mass ratio of the negative electrode material to the negative electrode active material layer. By setting the CB value, the performance of the positive electrode material and the negative electrode material can be fully utilized. The positive electrode material and the hard carbon material in the negative electrode material are reasonably matched. When the electrochemical device is a lithium-ion battery, when the CB value is too small, it may cause the positive electrode to provide Too many lithium ions in the negative electrode will cause lithium precipitation, and when the CB value is too large, it may lead to a decrease in energy density.
本申请还提出一种电子装置,包括上述任一项的电化学装置。The present application also proposes an electronic device, including any one of the above electrochemical devices.
本申请的实施例中电化学装置在-20℃的0.2C放电容量为A,电化学装置在25℃的0.2C放电容量为B,且70%≤A/B≤90%。本申请实施例中提出的电化学装置在-20℃的低温下具有较好的低温充放电性能,能够充入和放出较多的能量。In the examples of the present application, the 0.2C discharge capacity of the electrochemical device at -20°C is A, and the 0.2C discharge capacity of the electrochemical device at 25°C is B, and 70%≤A/B≤90%. The electrochemical device proposed in the examples of the present application has better low-temperature charge and discharge performance at a low temperature of -20° C., and can charge and release more energy.
具体实施方式detailed description
下面的实施例可以使本领域技术人员更全面地理解本申请,但不以任何方式限制本申请。The following examples can enable those skilled in the art to understand the present application more comprehensively, but do not limit the present application in any way.
电化学装置,例如锂离子电池,被广泛应用在各个领域,具有广泛使用场景。在低温下,电化学装置的充放电性能往往不能令人满意,期待进 一步的改进。Electrochemical devices, such as lithium-ion batteries, are widely used in various fields and have a wide range of usage scenarios. At low temperatures, the charge-discharge performance of electrochemical devices is often unsatisfactory, and further improvements are expected.
在本公开的说明中,“100%荷电状态”指的是将电化学装置恒电流充电至至最大设计电压下的状态,且包含静置(一般静置10min)后的状态,均视为满充状态,除非有特别说明,最大设计电压包括但不限于4.48V、4.5V、4.53V或4.45V,甚至更高电压。In the description of the present disclosure, "100% state of charge" refers to the state where the electrochemical device is charged to the maximum design voltage with a constant current, and includes the state after standing (generally standing for 10 minutes), which is regarded as Fully charged state, unless otherwise specified, the maximum design voltage includes but not limited to 4.48V, 4.5V, 4.53V or 4.45V, or even higher voltage.
在本公开的说明中,“0%荷电状态”指的是将电化学装置恒电流放电至最小设计电压下的状态,且包含静置(一般静置10min)后的状态,均视为满放状态,除非有特别说明,最大设计电压包括但不限于3.0V、2.8V、2.6V或2.0V,甚至更低电压。同样的,在本公开的说明中,50%荷电状态为包含静置(一般静置10min)后的状态。In the description of the present disclosure, "0% state of charge" refers to the state of constant current discharge of the electrochemical device to the minimum design voltage, and includes the state after standing (generally standing for 10 minutes), which is considered to be fully charged. In the discharge state, unless otherwise specified, the maximum design voltage includes but is not limited to 3.0V, 2.8V, 2.6V or 2.0V, or even lower voltage. Similarly, in the description of the present disclosure, the 50% state of charge includes the state after standing (generally standing for 10 minutes).
本申请的一些实施例提供了一种电化学装置,电化学装置在-20℃的0.2C放电容量为A,电化学装置在25℃的0.2C放电容量为B,且70%≤A/B≤90%。在一些实施例中,电化学装置在25℃的0.2C的放电容量B表征了电化学装置在常温下的充放电性能,电化学装置在-20℃的0.2C的放电容量A表征了电化学装置在低温下的充放电性能,A/B表征了电化学装置的充放电性能在低温下的保持率,由于70%≤A/B≤90%,这表明本申请实施例中提出的电化学装置在-20℃的低温下具有较好的充放电性能,能够充入和放出较多的能量,提高对电化学装置的低温下的充放电性能的满意度。Some embodiments of the present application provide an electrochemical device, the 0.2C discharge capacity of the electrochemical device at -20°C is A, the 0.2C discharge capacity of the electrochemical device at 25°C is B, and 70%≤A/B ≤90%. In some embodiments, the discharge capacity B of the electrochemical device at 0.2C at 25°C characterizes the charge and discharge performance of the electrochemical device at room temperature, and the discharge capacity A of the electrochemical device at 0.2C at -20°C characterizes the electrochemical device The charge and discharge performance of the device at low temperature, A/B characterizes the retention rate of the charge and discharge performance of the electrochemical device at low temperature, because 70%≤A/B≤90%, this shows that the electrochemical device proposed in the examples of this application The device has better charge and discharge performance at a low temperature of -20°C, can charge and release more energy, and improves the satisfaction with the charge and discharge performance of the electrochemical device at low temperature.
在本申请的一些实施例中,电化学装置在45℃的0.2C放电容量为C,103%≤C/B≤110%。在一些实施例中,电化学装置在45℃的0.2C放电容量为C表征了电化学装置在中高温下的充放电性能,103%≤C/B≤110%表明了电化学装置能够在中高温下充入和放出更多的能量,具有较好的中高温充放电性能。In some embodiments of the present application, the 0.2C discharge capacity of the electrochemical device at 45°C is C, 103%≤C/B≤110%. In some embodiments, the 0.2C discharge capacity of the electrochemical device at 45°C is C, which characterizes the charge and discharge performance of the electrochemical device at medium and high temperatures, and 103%≤C/B≤110% indicates that the electrochemical device can be used in medium and high temperature. Charge and release more energy at high temperature, and have better medium and high temperature charge and discharge performance.
在本申请的一些实施例中,电化学装置包括负极,电化学装置在50%荷电状态时负极的厚度为H 2,电化学装置在0%荷电状态时负极的厚度为H 1,(H 2-H 1)/H 1为0%至6%。一些实施例中,(H 2-H 1)/H 1表示了电化学装置在从0%荷电状态充电至50%荷电状态时负极的厚度增长率,该厚度增长率为0%至6%表示本申请实施例中的电化学装置的负极在充电过程中的膨胀较小,有利于提高电化学装置的充放电性能。 In some embodiments of the present application, the electrochemical device includes a negative electrode, the thickness of the negative electrode is H2 when the electrochemical device is at a state of charge of 50%, and the thickness of the negative electrode is H1 when the electrochemical device is at a state of charge of 0%, ( H 2 -H 1 )/H 1 is 0% to 6%. In some embodiments, (H 2 -H 1 )/H 1 represents the thickness growth rate of the negative electrode of the electrochemical device when it is charged from 0% state of charge to 50% state of charge, and the thickness growth rate is 0% to 6 % indicates that the expansion of the negative electrode of the electrochemical device in the embodiment of the present application is small during the charging process, which is conducive to improving the charge and discharge performance of the electrochemical device.
在本申请的一些实施例中,电化学装置包括负极,电化学装置在100%荷电状态时负极的厚度为H 3,电化学装置在0%荷电状态时负极的厚度为H 1,(H 3-H 1)/H 1为0%至8%。一些实施例中,(H 3-H 1)/H 1表示了电化学装置在从0%荷电状态充电至100%荷电状态时负极的厚度增长率,该厚度增长率为0%至8%表示本申请实施例中的电化学装置的负极在整个充电过程中的膨胀较小,有利于提高电化学装置的充放电性能。 In some embodiments of the present application, the electrochemical device includes a negative electrode, the thickness of the negative electrode is H 3 when the electrochemical device is in a 100% state of charge, and the thickness of the negative electrode is H 1 when the electrochemical device is in a 0% state of charge, ( H 3 -H 1 )/H 1 is 0% to 8%. In some embodiments, (H 3 -H 1 )/H 1 represents the thickness growth rate of the negative electrode of the electrochemical device when it is charged from 0% state of charge to 100% state of charge, and the thickness growth rate is 0% to 8 % means that the expansion of the negative electrode of the electrochemical device in the embodiment of the present application is small during the whole charging process, which is beneficial to improve the charge and discharge performance of the electrochemical device.
在本申请的一些实施例中,电化学装置包括负极,负极包括负极集流体和位于负极集流体的负极活性材料层,负极活性材料层的孔隙率为20%至50%。一些实施例中,负极活性材料层的孔隙率如果小于20%,说明负极材料之间的空间较小,可能导致负极材料与电解液的接触不充分,进而造成负极的性能无法充分发挥,当负极活性材料层的孔隙率超过50%时,可能因为负极材料的颗粒之间的间隙过大,导致负极材料的颗粒之间电接触不良,影响电化学装置的性能。一些实施例中,负极活性材料层的孔隙率为35%至50%,此时电化学装置的性能更优。In some embodiments of the present application, the electrochemical device includes a negative electrode, the negative electrode includes a negative electrode current collector and a negative electrode active material layer located on the negative electrode current collector, and the porosity of the negative electrode active material layer is 20% to 50%. In some embodiments, if the porosity of the negative electrode active material layer is less than 20%, it means that the space between the negative electrode materials is small, which may lead to insufficient contact between the negative electrode material and the electrolyte, and then cause the performance of the negative electrode to not be fully utilized. When the porosity of the active material layer exceeds 50%, the gap between the particles of the negative electrode material may be too large, resulting in poor electrical contact between the particles of the negative electrode material, which affects the performance of the electrochemical device. In some embodiments, the porosity of the negative electrode active material layer is 35% to 50%, and the performance of the electrochemical device is better at this time.
负极活性材料层的孔隙率测试:Porosity test of negative electrode active material layer:
取满放后锂离子电池,拆解后取出负极用DMC(乙烯碳酸酯)浸泡20min后,再依次用DMC、丙酮清洗,置于烘箱内,80℃烘干12h。用负极离子研磨制样后在SEM下观测,分别截取十张面积为A=20μm×20μm的含第一活性材料层截面SEM图片、第二活性材料层截面SEM图片,以及整个负极的截面SEM图片,用图像处理软件(Multiphase)计算得截面图内较暗部分孔隙的面积B,孔隙率=B/A×100%,然后计算十张SEM图片的孔隙率的平均值,即为负极活性材料层的孔隙率。Take a fully charged lithium-ion battery, disassemble it, take out the negative electrode and soak it in DMC (ethylene carbonate) for 20 minutes, then wash it with DMC and acetone in sequence, put it in an oven, and dry it at 80°C for 12 hours. After sample preparation by negative electrode ion milling, observe under SEM, and cut out ten pieces of SEM pictures with the area of A=20μm×20μm, including the cross-section SEM picture of the first active material layer, the cross-section SEM picture of the second active material layer, and the cross-section SEM picture of the entire negative electrode , use the image processing software (Multiphase) to calculate the area B of the darker part of the pore in the cross-sectional view, porosity=B/A×100%, and then calculate the average value of the porosity of ten SEM pictures, which is the negative electrode active material layer porosity.
在本申请的一些实施例中,电化学装置包括负极,负极包括负极集流体和位于负极集流体的负极活性材料层,负极活性材料层包括负极材料,负极材料包括硬碳,负极活性材料层与负极集流体之间的粘结力为10N/m至50N/m。一些实施例中,如果负极活性材料层与负极集流体之间的粘结力过小,可能导致在电化学装置的充放电过程中负极活性材料层与负极集流体之间剥离脱落或接触不良,不利于电子传导,影响测试性能。如果负极活性材 料层与负极集流体之间的粘结力过大,可能会需要使用过多的粘结剂,这可能不利于负极的电导率,影响动力学性能。In some embodiments of the present application, the electrochemical device includes a negative electrode, the negative electrode includes a negative electrode current collector and a negative electrode active material layer located on the negative electrode current collector, the negative electrode active material layer includes a negative electrode material, the negative electrode material includes hard carbon, the negative electrode active material layer and The binding force between negative electrode current collectors is 10 N/m to 50 N/m. In some embodiments, if the bonding force between the negative electrode active material layer and the negative electrode current collector is too small, it may cause peeling off or poor contact between the negative electrode active material layer and the negative electrode current collector during the charging and discharging process of the electrochemical device, It is not conducive to electron conduction and affects test performance. If the binding force between the negative electrode active material layer and the negative electrode current collector is too large, it may be necessary to use too much binder, which may be detrimental to the conductivity of the negative electrode and affect the kinetic performance.
负极活性材料层与负极集流体粘结力测试:Adhesion test between negative electrode active material layer and negative electrode current collector:
负极活性材料层与负极集流体的粘结力测试所用仪器的品牌为Instron,型号为33652,取负极(宽30mm×长度(100mm至160mm)),用双面胶纸(型号:3M9448A,宽度20mm×长度(90mm至150mm))固定于钢板上,将与负极等宽的纸带与负极一侧用胶纸固定,调整拉力机限位块至合适位置,将纸带向上翻折及滑移40mm,滑移速率为50mm/min,测试180°下(即反方向拉伸)负极活性材料层与负极集流体之间的粘结力。The brand of the instrument used for testing the adhesion between the negative electrode active material layer and the negative electrode current collector is Instron, the model is 33652, take the negative electrode (width 30mm × length (100mm to 160mm)), and use double-sided adhesive tape (model: 3M9448A, width 20mm) ×Length (90mm to 150mm)) is fixed on the steel plate, fix the paper tape with the same width as the negative electrode and the negative electrode side with adhesive tape, adjust the limit block of the tension machine to a suitable position, fold the paper tape upwards and slide 40mm , the slip rate is 50mm/min, and the adhesion force between the negative electrode active material layer and the negative electrode current collector is tested under 180° (that is, stretched in the opposite direction).
在本申请的一些实施例中,负极活性材料层的压实密度为0.9g/cm 3至1.25g/cm 3。负极活性材料层的压实密度的测试: In some embodiments of the present application, the compacted density of the negative electrode active material layer is 0.9 g/cm 3 to 1.25 g/cm 3 . Test of the compacted density of the negative electrode active material layer:
取完全放电的锂离子电池,拆解出负极,清洗,烘干,使用电子天平对一定面积S的负极(负极集流体的双面涂覆有负极活性材料层)进行称重,重量记为W1,并使用万分尺测得负极的厚度T1。使用溶剂洗掉负极活性材料层,烘干,测量负极集流体的重量,记为W2,并使用万分尺测得负极集流体的厚度T2。通过下式计算设置在负极集流体一侧的负极活性材料层的重量W0和厚度T0以及负极活性材料层的压实密度:Take a fully discharged lithium-ion battery, disassemble the negative electrode, wash, dry, use an electronic balance to weigh the negative electrode with a certain area S (both sides of the negative electrode current collector are coated with negative electrode active material layers), and record the weight as W1 , and use a micrometer to measure the thickness T1 of the negative electrode. Use a solvent to wash off the negative electrode active material layer, dry it, measure the weight of the negative electrode current collector, which is recorded as W2, and use a micrometer to measure the thickness T2 of the negative electrode current collector. The weight W0 and the thickness T0 of the negative electrode active material layer arranged on one side of the negative electrode current collector and the compacted density of the negative electrode active material layer are calculated by the following formula:
W0=(W1-W2)/2W0=(W1-W2)/2
T0=(T1-T2)/2T0=(T1-T2)/2
压实密度=W0/(T0×S)。Compacted density=W0/(T0×S).
一些实施例中,如果负极活性材料层的压实密度过小,将不利于电化学装置的体积能量密度,也不利于负极活性材料层中电子的传导。如果负极活性材料层的压实密度过大,可能会导致电解液无法充分浸润负极活性材料层,不利于充分发挥负极的性能。In some embodiments, if the compaction density of the negative electrode active material layer is too small, it will be unfavorable to the volumetric energy density of the electrochemical device, and it will also be unfavorable to the conduction of electrons in the negative electrode active material layer. If the compaction density of the negative electrode active material layer is too large, the electrolyte may not be able to fully infiltrate the negative electrode active material layer, which is not conducive to fully exerting the performance of the negative electrode.
在本申请的一些实施例中,负极材料的颗粒破碎率为10%至40%,一些实施例中,负极材料的颗粒破碎率为负极材料的破碎颗粒与负极材料的颗粒总数的比值,在统计负极材料的颗粒破碎率时,可以采用扫描电子显微镜(SEM)对负极活性材料层进行拍照,选取至少10个预定面积(10μm×10 μm)的区域,通过统计每个预定面积内的总颗粒数,然后再统计预定面积内破碎颗粒的数量,负极材料的颗粒破碎率=破碎颗粒的数量/总颗粒数,其中,破碎颗粒为可看见裂纹,即两个部分可完全重合的缝隙,说明颗粒破碎,总颗粒数统计时为粒径大于3μm的颗粒即进行统计,统计这些区域内负极材料的颗粒破碎率。电化学装置的负极在制造过程中通常会经过辊压,造成负极材料的颗粒部分破碎,少量的负极材料的颗粒破碎有利于增加与电解液的接触面积,提高倍率性能,如果负极材料的颗粒破碎率过高,将过度增加电解液的消耗,可选的,负极材料的颗粒破碎率为10%至25%,此时电化学装置的整体性能较好。In some embodiments of the present application, the particle crushing rate of the negative electrode material is 10% to 40%. In some embodiments, the particle crushing rate of the negative electrode material is the ratio of the broken particles of the negative electrode material to the total number of particles of the negative electrode material. In statistics For the particle breakage rate of the negative electrode material, a scanning electron microscope (SEM) can be used to take pictures of the negative electrode active material layer, select at least 10 areas with a predetermined area (10 μm × 10 μm), and count the total number of particles in each predetermined area , and then count the number of broken particles in the predetermined area, the particle breakage rate of the negative electrode material = the number of broken particles / the total number of particles, where the broken particles are visible cracks, that is, the gap where the two parts can completely overlap, indicating that the particles are broken , when the total particle number is counted, the particle diameter is larger than 3 μm, and the particle breakage rate of the negative electrode material in these areas is counted. The negative electrode of the electrochemical device is usually rolled during the manufacturing process, causing the particles of the negative electrode material to be partially broken. A small amount of particle breakage of the negative electrode material is conducive to increasing the contact area with the electrolyte and improving the rate performance. If the rate is too high, the consumption of the electrolyte will be excessively increased. Optionally, the particle breakage rate of the negative electrode material is 10% to 25%. At this time, the overall performance of the electrochemical device is better.
在本申请的一些实施例中,负极材料的X射线衍射图谱中,在18°至30°之间具有一个衍射峰,衍射峰的半高峰宽为4°至10°。在一些实施例中,在18°至30°之间只有一个半高宽为4°至10°的衍射峰,一些实施例中,负极材料可以包括硬碳。In some embodiments of the present application, in the X-ray diffraction pattern of the negative electrode material, there is a diffraction peak between 18° and 30°, and the half-height width of the diffraction peak is 4° to 10°. In some embodiments, there is only one diffraction peak with a full width at half maximum of 4° to 10° between 18° and 30°. In some embodiments, the negative electrode material may include hard carbon.
在本申请的一些实施例中,负极材料的微晶片层间距为0.34nm至0.4nm。一些实施例中,负极材料包括碳材料,微晶片层间距为0.34nm至0.4nm说明碳材料为无定形碳。可选的,负极材料的微晶片层间距为0.38nm至0.39nm,此时负极材料的动力学性能较好,负极膨胀率较小,当负极材料的微晶片层间距过小时,离子在微晶片层之间扩散的阻力较大,微晶片层易于被离子撑开,导致负极整体膨胀。当微晶片层间距过大时,可能存在部分溶剂共嵌入的状况,破坏负极材料结构,影响整体电性能。In some embodiments of the present application, the distance between the microchip layers of the negative electrode material is 0.34 nm to 0.4 nm. In some embodiments, the negative electrode material includes carbon material, and the distance between the microchip layers is 0.34 nm to 0.4 nm, indicating that the carbon material is amorphous carbon. Optionally, the microchip layer spacing of the negative electrode material is 0.38nm to 0.39nm. At this time, the dynamic performance of the negative electrode material is better, and the expansion rate of the negative electrode is small. When the microchip layer spacing of the negative electrode material is too small, the ions in the microchip The resistance to diffusion between layers is relatively large, and the microchip layer is easily stretched by ions, resulting in the overall expansion of the negative electrode. When the interlayer spacing of the microchips is too large, some solvents may be co-embedded, which will destroy the structure of the negative electrode material and affect the overall electrical performance.
在本申请的一些实施例中,电化学装置在25℃的1C放电容量为D,0.9<D/B<1。一些实施例中,电化学装置的1C倍率下的充放电性能相比于0.2C下的充放电性能几乎不变,电化学装置具有良好的倍率性能。In some embodiments of the present application, the 1C discharge capacity of the electrochemical device at 25° C. is D, 0.9<D/B<1. In some embodiments, the charge and discharge performance of the electrochemical device at a rate of 1C is almost the same as that at a rate of 0.2C, and the electrochemical device has good rate performance.
在本申请的一些实施例中,电化学装置在25℃的5C放电容量为E,99%≤E/B≤105%。一些实施例中,电化学装置在温度为25℃的情况下,5C倍率下的放电容量大于0.2C下的放电容量,这表明电化学装置具有良好的大倍率充放电性能。In some embodiments of the present application, the 5C discharge capacity of the electrochemical device at 25° C. is E, 99%≤E/B≤105%. In some embodiments, when the temperature of the electrochemical device is 25° C., the discharge capacity at 5C rate is greater than the discharge capacity at 0.2C, which indicates that the electrochemical device has good high-rate charge-discharge performance.
在一些实施例中,对电化学装置进行三电极电位监控,在以电压为纵坐标,荷电状态为横坐标作图,负极脱锂曲线在0.3V至0.8V为斜坡区(斜坡 区指电化学曲线与0V水平线夹角大于30°,即相比于初始曲线,为明显的上升趋势),负极脱锂曲线在0.2V以下的荷电状态占比F为30%至80%。在一些实施例中,斜坡区为硬碳材料的本征特性,不同负极材料的脱锂曲线在0.2V以下的荷电状态占比F不同,在负极脱锂曲线在0.2V以下的荷电状态占比F为30%至80%时电化学装置的动力学性能较好,但是若负极脱锂曲线在0.2V以下的荷电状态占比F大于80%时,电化学装置的整体电压低,能量密度降低。In some embodiments, the three-electrode potential is monitored on the electrochemical device, and the voltage is taken as the ordinate, and the state of charge is used as the abscissa to draw a graph, and the delithiation curve of the negative electrode is a slope area between 0.3V and 0.8V (the slope area refers to the electric The angle between the chemical curve and the 0V horizontal line is greater than 30°, that is, compared with the initial curve, it is an obvious upward trend), and the charge state ratio F of the negative electrode delithiation curve below 0.2V is 30% to 80%. In some embodiments, the slope area is an intrinsic characteristic of the hard carbon material, and the state of charge ratio F of the delithiation curve of different negative electrode materials is different below 0.2V. The kinetic performance of the electrochemical device is better when the proportion F is 30% to 80%, but if the charge state proportion F of the negative electrode delithiation curve is below 0.2V is greater than 80%, the overall voltage of the electrochemical device is low, Energy density is reduced.
在一些实施例中,电化学装置包括正极和负极,正极包括正极集流体和位于正极流体上的正极活性材料层,负极包括负极集流体和位于负极集流体上的负极活性材料层,单位面积的单面正极活性材料层的重量为M 1,单位面积的单面负极活性材料层的重量为M 2,M 1/M 2为2至6。一些实施例中,正极集流体的一面或两面可以具有正极活性材料层,M 1为正极集流体上一面上单位面积正极活性材料层的重量,类似的,负极集流体的一面或两面具有负极活性材料层,M 2为负极集流体一面上单位面积负极活性材料层的重量。 In some embodiments, the electrochemical device includes a positive electrode and a negative electrode, the positive electrode includes a positive electrode current collector and a positive electrode active material layer on the positive electrode fluid, and the negative electrode includes a negative electrode current collector and a negative electrode active material layer on the negative electrode current collector. The weight of the single-sided positive electrode active material layer is M 1 , the weight of the single-sided negative electrode active material layer per unit area is M 2 , and M 1 /M 2 is 2 to 6. In some embodiments, one or both sides of the positive electrode current collector can have a positive electrode active material layer, and M1 is the weight of the positive electrode active material layer per unit area on one side of the positive electrode current collector. Similarly, one or both sides of the negative electrode current collector have a negative active material layer Material layer, M2 is the weight of the negative electrode active material layer per unit area on one side of the negative electrode current collector.
在一些实施例中,电化学装置的CB值为0.9至1.1,可选的,CB值为0.95至1.06;其中,CB值为相同面积下负极容量与正极容量之间的比值。一些实施例中,通过设置CB值,能够充分发挥正极材料和负极材料的性能,不会造成浪费,在电化学装置为锂离子电池时,在CB值过小时,可能导致正极提供的锂离子过多,造成负极析锂,在CB值过大时,可能导致能量密度下降。其中,CB=负极容量/正极容量,所述的负极容量为(CW 负极×克容量 负极×活性材料百分含量 负极),所述的正极容量为(CW 正极×克容量 正极×活性材料百分含量 正极),所述的CW 负极和CW 正极为涂布时,称取1540.25mm 2面积上的负极活性材料层的重量和正极活性材料层的重量,其中,CW及活性材料百分含量的获取方式为将电池拆出正极和负极,分别在平整的正极和负极上冲小圆片(如1540.25mm 2面积),并称量活性材料层的重量即为CW(涂膜区重量-空铜铝箔重量得到)。然后将小圆片加浓盐酸消解,并过滤,烘干,然后计算得出活性材料在活性材料层的百分比(盐酸消解后烘干的待测物重量/盐酸消解前待测物重量)。 In some embodiments, the CB value of the electrochemical device is 0.9 to 1.1, optionally, the CB value is 0.95 to 1.06; wherein, the CB value is the ratio of the negative electrode capacity to the positive electrode capacity under the same area. In some embodiments, by setting the CB value, the performance of the positive electrode material and the negative electrode material can be fully utilized without causing waste. When the electrochemical device is a lithium-ion battery, if the CB value is too small, the lithium ions provided by the positive electrode may be too high. If the value is too large, it will cause the negative electrode to precipitate lithium, and when the CB value is too large, it may lead to a decrease in energy density. Wherein, CB=negative electrode capacity/positive electrode capacity, the negative electrode capacity is (CW negative electrode ×gram capacity negative electrode ×active material percentage content negative electrode ), and the described positive electrode capacity is (CW positive electrode ×gram capacity positive electrode ×active material percentage content positive electrode ), when the CW negative electrode and CW positive electrode are coated, weigh the weight of the negative electrode active material layer and the weight of the positive electrode active material layer on the area of 1540.25mm , wherein, the acquisition of CW and active material percentage The method is to remove the positive and negative electrodes from the battery, punch small discs (such as 1540.25mm2 area) on the flat positive and negative electrodes respectively, and weigh the weight of the active material layer, which is CW (weight of coating film area - empty copper and aluminum foil weight obtained). Then the small disc is digested with concentrated hydrochloric acid, filtered, dried, and then the percentage of the active material in the active material layer is calculated (the weight of the sample dried after hydrochloric acid digestion/the weight of the sample before hydrochloric acid digestion).
克容量 负极和克容量 正极测试: Gram capacity negative electrode and gram capacity positive electrode test:
第一步:制作纽扣型电池:将负极(正极)裁切成Φ(直径)=14mm圆片作为工作电极,以Φ(直径)=18mm金属锂作为对电极及参比电极,两者中间用Φ(直径)=20mm PE隔离膜隔开,滴加适量本申请的电解液,装配得到CR2430型纽扣电池。Step 1: Make a button-type battery: cut the negative electrode (positive electrode) into Φ (diameter) = 14mm disc as the working electrode, use Φ (diameter) = 18mm metal lithium as the counter electrode and reference electrode, and use it in between Φ (diameter)=20mm PE isolation film is separated, and the electrolytic solution of the present application is added dropwise, assembles and obtains CR2430 button battery.
第二步:克容量测试:取装配好的纽扣电池,确保开路电压(OCV)正常,每组至少包含4个平行样。纽扣电池的电压窗口设定在0V至2.5V。在25℃先静置1h,再以0.05C/50μA/20μA三阶段小电流对电池进行放电,负极实现SEI(固体电解质界面膜)成膜并记录嵌锂容量(正极实现成膜并记录嵌锂容量)。随后以0.1C电流将电池充电至2.5V,记录负极(正极)脱锂容量,该脱锂容量即负极材料(正极材料)的克容量 负极(克容量 正极)。 Step 2: Gram capacity test: Take the assembled button battery to ensure that the open circuit voltage (OCV) is normal, and each group contains at least 4 parallel samples. The voltage window for the coin cell is set from 0V to 2.5V. Let stand at 25°C for 1 hour, and then discharge the battery with a three-stage low current of 0.05C/50μA/20μA. The negative electrode realizes SEI (solid electrolyte interfacial film) film formation and records the lithium intercalation capacity (the positive electrode realizes film formation and records lithium intercalation. capacity). Then charge the battery to 2.5V with a current of 0.1C, and record the delithiation capacity of the negative electrode (positive electrode), which is the gram capacity of the negative electrode material (positive electrode material) negative electrode (gram capacity positive electrode ).
本申请一些实施例中负极材料包括碳材料,下面简要地描述负极材料的制备过程以更好地理解本申请,但这仅是示例性的,而不用于限制本申请。将原料1(例如酚醛树脂)溶解于溶剂1(例如乙醇)搅拌一段时间得到混合液,之后将混合液转移至水热反应釜中,在180℃的条件下进行水热反应,待温度冷却,取出固体部分烘干。并放至箱式炉按一定的烧结方式对材料进行烧结,得到负极材料。一些实施例中,溶剂1还可以为:水、丙酮、甲醇、二氯甲烷、乙酸乙酯、己烷、石油醚、甲苯或N-甲基吡咯烷酮。一些实施例中,原料1为可溶材料时可以为:环氧树脂、脲醛树脂、氨基树脂类、醚基树脂类、聚酯树脂类、蔗糖或葡萄糖。当原料1为不溶材料时,可直接进入烧结步骤,此时原料1包含:生物质类如果壳,秸秆等,木质素纤维素,淀粉,聚氯乙烯,聚乙烯,聚丙烯,聚苯乙烯ABS塑料等。应该理解,该制备方法仅是示例性的,还可以采用其他合适的制备方法。一些实施例中,采用根本申请提出的负极材料的电化学装置具有优异的低温充放电性能、大倍率性能和较小的膨胀率。In some embodiments of the present application, the negative electrode material includes carbon materials. The preparation process of the negative electrode material is briefly described below to better understand the present application, but this is only exemplary and not intended to limit the present application. Dissolve raw material 1 (such as phenolic resin) in solvent 1 (such as ethanol) and stir for a period of time to obtain a mixed solution, then transfer the mixed solution to a hydrothermal reaction kettle, perform a hydrothermal reaction at 180°C, and wait for the temperature to cool. Remove the solid part and dry it. And put it into a box-type furnace to sinter the material according to a certain sintering method to obtain the negative electrode material. In some embodiments, the solvent 1 can also be: water, acetone, methanol, dichloromethane, ethyl acetate, hexane, petroleum ether, toluene or N-methylpyrrolidone. In some embodiments, when the raw material 1 is a soluble material, it may be: epoxy resin, urea-formaldehyde resin, amino resin, ether-based resin, polyester resin, sucrose or glucose. When the raw material 1 is an insoluble material, it can directly enter the sintering step. At this time, the raw material 1 includes: biomass such as shells, straw, etc., lignocellulose, starch, polyvinyl chloride, polyethylene, polypropylene, polystyrene ABS Plastic etc. It should be understood that this preparation method is only exemplary, and other suitable preparation methods can also be used. In some embodiments, the electrochemical device using the negative electrode material proposed in the basic application has excellent low-temperature charge and discharge performance, high rate performance and small expansion rate.
在一些实施例中,负极活性材料层中还可以包括导电剂和粘结剂。在一些实施例中,负极活性材料层中的导电剂可以包括导电炭黑、科琴黑、片层石墨、石墨烯、碳纳米管或碳纤维中的至少一种。在一些实施例中,负极活性材料层中的粘结剂可以包括羧甲基纤维素(CMC)、聚丙烯酸、聚乙烯基吡咯烷酮、聚苯胺、聚酰亚胺、聚酰胺酰亚胺、聚硅氧烷、丁苯橡胶、环氧树脂、聚酯树脂、聚氨酯树脂或聚芴中的至少一种。在一些实施例中, 负极活性材料层中的负极材料、导电剂和粘结剂的质量比可以为(78至98.5):(0.1至10):(0.1至10)。负极材料可以是硅基材料和其他材料的混合品。应该理解,以上所述仅是示例,可以采用任何其他合适的材料和质量比。在一些实施例中,负极集流体可以采用铜箔、镍箔或碳基集流体中的至少一种。In some embodiments, a conductive agent and a binder may also be included in the negative electrode active material layer. In some embodiments, the conductive agent in the negative electrode active material layer may include at least one of conductive carbon black, Ketjen black, flake graphite, graphene, carbon nanotubes, or carbon fibers. In some embodiments, the binder in the negative active material layer may include carboxymethylcellulose (CMC), polyacrylic acid, polyvinylpyrrolidone, polyaniline, polyimide, polyamideimide, polysilicon At least one of oxane, styrene-butadiene rubber, epoxy resin, polyester resin, polyurethane resin or polyfluorene. In some embodiments, the mass ratio of the negative electrode material, the conductive agent and the binder in the negative electrode active material layer may be (78 to 98.5):(0.1 to 10):(0.1 to 10). The negative electrode material can be a mixture of silicon-based materials and other materials. It should be understood that the above description is only an example, and any other suitable materials and mass ratios may be used. In some embodiments, the negative electrode current collector may use at least one of copper foil, nickel foil, or carbon-based current collector.
在一些实施例中,正极包括正极集流体和设置在正极集流体上的正极活性材料层,正极活性材料层可以包括正极材料。正极材料包括能够吸收和释放锂(Li)的正极材料。能够吸收/释放锂的正极材料的例子可以包括钴酸锂、镍钴锰酸锂、镍钴铝酸锂、锰酸锂、磷酸锰铁锂、磷酸钒锂、磷酸钒氧锂、磷酸铁锂、钛酸锂和富锂锰基材料。In some embodiments, the positive electrode includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, and the positive electrode active material layer may include a positive electrode material. The positive electrode material includes a positive electrode material capable of absorbing and releasing lithium (Li). Examples of positive electrode materials capable of absorbing/releasing lithium may include lithium cobalt oxide, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium manganate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium iron phosphate, Lithium titanate and lithium-rich manganese-based materials.
具体的,钴酸锂的化学式可以如化学式1:Specifically, the chemical formula of lithium cobalt oxide can be as chemical formula 1:
Li xCo aM1 bO 2-c        化学式1 Li x Co a M1 b O 2-c chemical formula 1
其中M1表示选自镍(Ni)、锰(Mn)、镁(Mg)、铝(Al)、硼(B)、钛(Ti)、钒(V)、铬(Cr)、铁(Fe)、铜(Cu)、锌(Zn)、钼(Mo)、锡(Sn)、钙(Ca)、锶(Sr)、钨(W)、钇(Y)、镧(La)、锆(Zr)和硅(Si)中的至少一种,x、a、b和c值分别在以下范围内:0.8≤x≤1.2、0.8≤a≤1、0≤b≤0.2、-0.1≤c≤0.2;Where M1 means selected from nickel (Ni), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), Copper (Cu), Zinc (Zn), Molybdenum (Mo), Tin (Sn), Calcium (Ca), Strontium (Sr), Tungsten (W), Yttrium (Y), Lanthanum (La), Zirconium (Zr) and At least one of silicon (Si), the values of x, a, b and c are respectively in the following ranges: 0.8≤x≤1.2, 0.8≤a≤1, 0≤b≤0.2, -0.1≤c≤0.2;
镍钴锰酸锂或镍钴铝酸锂的化学式可以如化学式2:The chemical formula of lithium nickel cobalt manganate or lithium nickel cobalt aluminate can be as chemical formula 2:
Li yNi dM2 eO 2-f        化学式2 Li y Ni d M2 e O 2-f chemical formula 2
其中M2表示选自钴(Co)、锰(Mn)、镁(Mg)、铝(Al)、硼(B)、钛(Ti)、钒(V)、铬(Cr)、铁(Fe)、铜(Cu)、锌(Zn)、钼(Mo)、锡(Sn)、钙(Ca)、锶(Sr)、钨(W)、锆(Zr)和硅(Si)中的至少一种,y、d、e和f值分别在以下范围内:0.8≤y≤1.2、0.3≤d≤0.98、0.02≤e≤0.7、-0.1≤f≤0.2;Wherein M2 means selected from cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), at least one of copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), zirconium (Zr), and silicon (Si), The values of y, d, e and f are respectively in the following ranges: 0.8≤y≤1.2, 0.3≤d≤0.98, 0.02≤e≤0.7, -0.1≤f≤0.2;
锰酸锂的化学式可以如化学式3:The chemical formula of lithium manganate can be as chemical formula 3:
Li zMn 2-gM3 gO 4-h       化学式3 Li z Mn 2-g M3 g O 4-h chemical formula 3
其中M3表示选自钴(Co)、镍(Ni)、镁(Mg)、铝(Al)、硼(B)、钛(Ti)、钒(V)、铬(Cr)、铁(Fe)、铜(Cu)、锌(Zn)、钼(Mo)、 锡(Sn)、钙(Ca)、锶(Sr)和钨(W)中的至少一种,z、g和h值分别在以下范围内:0.8≤z≤1.2、0≤g<1.0和-0.2≤h≤0.2。Where M3 means selected from cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), At least one of copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr) and tungsten (W), the values of z, g and h are respectively in the following ranges Inside: 0.8≤z≤1.2, 0≤g<1.0 and -0.2≤h≤0.2.
在一些实施例中,正极活性材料层还可以包括导电剂。在一些实施例中,正极活性材料层中的导电剂可以包括导电炭黑、科琴黑、片层石墨、石墨烯、碳纳米管或碳纤维中的至少一种。在一些实施例中,正极活性材料层还可以包括粘结剂,正极活性材料层中的粘结剂可以包括羧甲基纤维素(CMC)、聚丙烯酸、聚乙烯基吡咯烷酮、聚苯胺、聚酰亚胺、聚酰胺酰亚胺、聚硅氧烷、丁苯橡胶、环氧树脂、聚酯树脂、聚氨酯树脂或聚芴中的至少一种。在一些实施例中,正极活性材料层中的正极材料、导电剂和粘结剂的质量比可以为(80至99):(0.1至10):(0.1至10)。在一些实施例中,正极活性材料层的厚度可以为10μm至500μm。应该理解,以上所述仅是示例,正极活性材料层可以采用任何其他合适的材料、厚度和质量比。在一些实施例中,正极的正极集流体可以采用Al箔,当然,也可以采用本领域常用的其他集流体。在一些实施例中,正极的正极集流体的厚度可以为1μm至50μm。在一些实施例中,正极活性材料层可以仅涂覆在正极集流体的部分区域上。In some embodiments, the positive active material layer may further include a conductive agent. In some embodiments, the conductive agent in the positive active material layer may include at least one of conductive carbon black, Ketjen black, flake graphite, graphene, carbon nanotubes, or carbon fibers. In some embodiments, the positive electrode active material layer can also include a binder, and the binder in the positive electrode active material layer can include carboxymethylcellulose (CMC), polyacrylic acid, polyvinylpyrrolidone, polyaniline, polyamide At least one of imine, polyamideimide, polysiloxane, styrene-butadiene rubber, epoxy resin, polyester resin, polyurethane resin or polyfluorene. In some embodiments, the mass ratio of the positive electrode material, the conductive agent and the binder in the positive electrode active material layer may be (80 to 99):(0.1 to 10):(0.1 to 10). In some embodiments, the positive active material layer may have a thickness of 10 μm to 500 μm. It should be understood that the above description is only an example, and any other suitable material, thickness and mass ratio may be used for the positive electrode active material layer. In some embodiments, Al foil may be used as the positive current collector of the positive electrode, and of course, other current collectors commonly used in the art may also be used. In some embodiments, the thickness of the positive current collector of the positive electrode may be 1 μm to 50 μm. In some embodiments, the positive active material layer may be coated only on a partial area of the positive current collector.
在一些实施例中,一些实施例中,电化学装置包括设置在正极和负极之间的隔离膜。隔离膜包括聚乙烯、聚丙烯、聚偏氟乙烯、聚对苯二甲酸乙二醇酯、聚酰亚胺或芳纶中的至少一种。例如,聚乙烯包括选自高密度聚乙烯、低密度聚乙烯或超高分子量聚乙烯中的至少一种。尤其是聚乙烯和聚丙烯,它们对防止短路具有良好的作用,并可以通过关断效应改善电池的稳定性。在一些实施例中,隔离膜的厚度在约5μm至50μm的范围内。In some embodiments, the electrochemical device includes a separator disposed between the positive electrode and the negative electrode. The isolation film includes at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyethylene terephthalate, polyimide or aramid. For example, polyethylene includes at least one selected from high-density polyethylene, low-density polyethylene, or ultra-high molecular weight polyethylene. Especially polyethylene and polypropylene, which have a good effect on preventing short circuits and can improve the stability of the battery through the shutdown effect. In some embodiments, the thickness of the isolation film is in the range of about 5 μm to 50 μm.
在一些实施例中,隔离膜表面还可以包括多孔层,多孔层设置在隔离膜的至少一个表面上,多孔层包括无机颗粒和粘结剂,无机颗粒选自氧化铝(Al 2O 3)、氧化硅(SiO 2)、氧化镁(MgO)、氧化钛(TiO 2)、二氧化铪(HfO 2)、氧化锡(SnO 2)、二氧化铈(CeO 2)、氧化镍(NiO)、氧化锌(ZnO)、氧化钙(CaO)、氧化锆(ZrO 2)、氧化钇(Y 2O 3)、碳化硅(SiC)、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙或硫酸钡中的至少一种。在一些实施例中,隔离膜的孔具有在约0.01μm至1μm的范围 的直径。多孔层的粘结剂选自聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素钠、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。隔离膜表面的多孔层可以提升隔离膜的耐热性能、抗氧化性能和电解质浸润性能,增强隔离膜与极片之间的粘结性。 In some embodiments, the surface of the isolation membrane may also include a porous layer, the porous layer is arranged on at least one surface of the isolation membrane, the porous layer includes inorganic particles and a binder, and the inorganic particles are selected from alumina (Al 2 O 3 ), Silicon oxide (SiO 2 ), magnesium oxide (MgO), titanium oxide (TiO 2 ), hafnium oxide (HfO 2 ), tin oxide (SnO 2 ), cerium oxide (CeO 2 ), nickel oxide (NiO), oxide Zinc (ZnO), calcium oxide (CaO), zirconia (ZrO 2 ), yttrium oxide (Y 2 O 3 ), silicon carbide (SiC), boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide or sulfuric acid at least one of barium. In some embodiments, the pores of the isolation membrane have a diameter in the range of about 0.01 μm to 1 μm. The binder of the porous layer is selected from polyvinylidene fluoride, copolymer of vinylidene fluoride-hexafluoropropylene, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, poly At least one of vinylpyrrolidone, polyvinyl ether, polymethylmethacrylate, polytetrafluoroethylene or polyhexafluoropropylene. The porous layer on the surface of the separator can improve the heat resistance, oxidation resistance and electrolyte wettability of the separator, and enhance the adhesion between the separator and the pole piece.
在本申请的一些实施例中,电化学装置的为卷绕式、堆叠式或折叠式。在一些实施例中,电化学装置的正极和/或负极可以是卷绕或堆叠式形成的多层结构,也可以是单层正极、隔离膜、单层负极叠加的单层结构。In some embodiments of the present application, the electrochemical device is wound, stacked or folded. In some embodiments, the positive electrode and/or negative electrode of the electrochemical device may be a wound or stacked multi-layer structure, or a single-layer structure in which a single-layer positive electrode, a separator, and a single-layer negative electrode are stacked.
在一些实施例中,电化学装置包括锂离子电池,但是本申请不限于此。在一些实施例中,电化学装置还可以包括电解质。电解质可以是凝胶电解质、固态电解质和电解液中的一种或多种,电解液包括锂盐和非水溶剂。锂盐选自LiPF 6、LiBF 4、LiAsF 6、LiClO 4、LiB(C 6H 5) 4、LiCH 3SO 3、LiCF 3SO 3、LiN(SO 2CF 3) 2、LiC(SO 2CF 3) 3、LiSiF 6、LiBOB或者二氟硼酸锂中的一种或多种。例如,锂盐选用LiPF 6,因为它具有高的离子导电率并可以改善循环特性。非水溶剂可为碳酸酯化合物、基于酯的化合物、基于醚的化合物、基于酮的化合物、基于醇的化合物、非质子溶剂或它们的组合。碳酸酯化合物可为链状碳酸酯化合物、环状碳酸酯化合物、氟代碳酸酯化合物或其组合。 In some embodiments, the electrochemical device includes a lithium-ion battery, although the present application is not limited thereto. In some embodiments, the electrochemical device may also include an electrolyte. The electrolyte may be one or more of a gel electrolyte, a solid electrolyte and an electrolytic solution, and the electrolytic solution includes a lithium salt and a non-aqueous solvent. The lithium salt is selected from LiPF 6 , LiBF 4 , LiAsF 6 , LiClO 4 , LiB(C 6 H 5 ) 4 , LiCH 3 SO 3 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 , LiC(SO 2 CF 3 ) 3 , LiSiF 6 , LiBOB or one or more of lithium difluoroborate. For example, LiPF 6 is selected as a lithium salt because it has high ion conductivity and can improve cycle characteristics. The non-aqueous solvent may be a carbonate compound, an ester-based compound, an ether-based compound, a ketone-based compound, an alcohol-based compound, an aprotic solvent, or a combination thereof. The carbonate compound can be a chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate compound or a combination thereof.
链状碳酸酯化合物的实例为碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(MEC)及其组合。所述环状碳酸酯化合物的实例为碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、碳酸乙烯基亚乙酯(VEC)或者其组合。所述氟代碳酸酯化合物的实例为碳酸氟代亚乙酯(FEC)、碳酸1,2-二氟亚乙酯、碳酸1,1-二氟亚乙酯、碳酸1,1,2-三氟亚乙酯、碳酸1,1,2,2-四氟亚乙酯、碳酸1-氟-2-甲基亚乙酯、碳酸1-氟-1-甲基亚乙酯、碳酸1,2-二氟-1-甲基亚乙酯、碳酸1,1,2-三氟-2-甲基亚乙酯、碳酸三氟甲基亚乙酯或者其组合。Examples of chain carbonate compounds are diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methyl carbonate Ethyl Ester (MEC) and combinations thereof. Examples of the cyclic carbonate compound are ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylethylene carbonate (VEC), or combinations thereof. Examples of the fluorocarbonate compound are fluoroethylene carbonate (FEC), 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate, Fluoroethylene carbonate, 1,1,2,2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-carbonic acid - Difluoro-1-methylethylene carbonate, 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate, or a combination thereof.
羧酸酯化合物的实例为乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸叔丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、癸内酯、戊内酯、甲瓦 龙酸内酯、己内酯、甲酸甲酯或者其组合。Examples of carboxylate compounds are methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, γ-butyrolactone, decanolactone, Valerolactone, mevalonolactone, caprolactone, methyl formate, or combinations thereof.
醚化合物的实例为二丁醚、四甘醇二甲醚、二甘醇二甲醚、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、2-甲基四氢呋喃、四氢呋喃或者其组合。Examples of ether compounds are dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxy ethyl ethane, 2-methyltetrahydrofuran, tetrahydrofuran or a combination thereof.
其它有机溶剂的实例为二甲亚砜、1,2-二氧戊环、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、N-甲基-2-吡咯烷酮、甲酰胺、二甲基甲酰胺、乙腈、磷酸三甲酯、磷酸三乙酯、磷酸三辛酯、和磷酸酯或者其组合。Examples of other organic solvents are dimethylsulfoxide, 1,2-dioxolane, sulfolane, methylsulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, methyl Amides, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphate esters or combinations thereof.
在本申请的一些实施例中,以锂离子电池为例,将正极、隔离膜、负极按顺序卷绕或堆叠成电极件,之后装入例如铝塑膜中进行封装,注入电解液,化成、封装,即制成锂离子电池。然后,对制备的锂离子电池进行性能测试。In some embodiments of the present application, taking a lithium-ion battery as an example, the positive electrode, separator, and negative electrode are sequentially wound or stacked into an electrode part, and then packed into an aluminum-plastic film for packaging, injected with an electrolyte, formed, Encapsulation, that is, made of lithium-ion batteries. Then, performance tests were performed on the prepared lithium-ion batteries.
本领域的技术人员将理解,以上描述的电化学装置(例如,锂离子电池)的制备方法仅是实施例。在不背离本申请公开的内容的基础上,可以采用本领域常用的其他方法。It will be appreciated by those skilled in the art that the above-described fabrication methods of electrochemical devices (eg, lithium-ion batteries) are examples only. Other methods commonly used in the art can be adopted without departing from the content disclosed in the present application.
本申请的实施例还提供了包括上述电化学装置的电子装置。本申请实施例的电子装置没有特别限定,其可以是用于现有技术中已知的任何电子装置。在一些实施例中,电子装置可以包括,但不限于,笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、无人机、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机、家庭用大型蓄电池和锂离子电容器等。Embodiments of the present application also provide an electronic device including the above electrochemical device. The electronic device in the embodiment of the present application is not particularly limited, and it may be used in any electronic device known in the prior art. In some embodiments, electronic devices may include, but are not limited to, notebook computers, pen-based computers, mobile computers, e-book players, cellular phones, portable fax machines, portable copiers, portable printers, headsets, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic organizers, calculators, memory cards, portable tape recorders, radios, backup power supplies, motors, cars, motorcycles, power-assisted bicycles, bicycles, Unmanned aerial vehicles, lighting equipment, toys, game consoles, clocks, electric tools, flashlights, cameras, large household storage batteries and lithium-ion capacitors, etc.
下面列举了一些具体实施例和对比例以更好地对本申请进行说明,其中,采用锂离子电池作为示例。Some specific examples and comparative examples are listed below to better illustrate the present application, wherein a lithium-ion battery is used as an example.
实施例1Example 1
正极的制备:将钴酸锂、导电炭黑(Super P)、聚偏二氟乙烯(PVDF)按照重量比97.5:1.0:1.5进行混合,加入N-甲基吡咯烷酮(NMP)作为溶 剂,搅拌均匀。将浆料均匀涂覆在正极集流体铝箔上,涂覆厚度为80μm,经过干燥、冷压、裁切后得到正极。Preparation of the positive electrode: mix lithium cobaltate, conductive carbon black (Super P), and polyvinylidene fluoride (PVDF) according to a weight ratio of 97.5:1.0:1.5, add N-methylpyrrolidone (NMP) as a solvent, and stir evenly . The slurry was uniformly coated on the positive electrode current collector aluminum foil with a coating thickness of 80 μm, and the positive electrode was obtained after drying, cold pressing and cutting.
负极的制备:将环氧树脂溶解于乙醇搅拌一段时间得到混合液,之后加入固化剂(间苯二胺)(环氧树脂:固化剂质量比=10:1)将混合液转移至水热反应釜中,在180℃的条件下进行水热反应,待温度冷却,取出固体部分。并放至箱式炉,在通氮气的条件下按5℃/min升温至200℃恒温1h,然后5℃/min升温至900℃2h,自然冷却,破碎得到负极材料。将负极材料、导电炭黑和丁苯橡胶或改性PAA按重量比96:1.5:2.5的比例溶于去离子水中,形成负极浆料。采用铜箔6μm作为负极的集流体,将负极浆料涂覆于负极的集流体上,涂覆负极活性材料层的厚度为50μm,干燥后,在压力30吨,辊隙为100μm的条件下冷压(辊压),裁切后得到负极,得到负极活性材料层的孔隙率为30%。Preparation of negative electrode: Dissolve epoxy resin in ethanol and stir for a period of time to obtain a mixed solution, then add a curing agent (m-phenylenediamine) (epoxy resin: curing agent mass ratio = 10:1) to transfer the mixed solution to the hydrothermal reaction In the still, carry out hydrothermal reaction under the condition of 180°C, wait for the temperature to cool down, and take out the solid part. Put it into a box furnace, raise the temperature to 200°C at 5°C/min for 1 hour under the condition of blowing nitrogen, then raise the temperature to 900°C for 2 hours at 5°C/min, cool naturally, and crush to obtain the negative electrode material. The negative electrode material, conductive carbon black and styrene-butadiene rubber or modified PAA are dissolved in deionized water at a weight ratio of 96:1.5:2.5 to form negative electrode slurry. Copper foil 6 μm is used as the current collector of the negative electrode, and the negative electrode slurry is coated on the current collector of the negative electrode. The thickness of the coated negative electrode active material layer is 50 μm. After drying, it is cooled under the conditions of a pressure of 30 tons and a roll gap of 100 μm Pressing (rolling) and cutting to obtain the negative electrode, and the porosity of the negative electrode active material layer is 30%.
隔离膜的制备:隔离膜为7μm厚的聚乙烯(PE)。Preparation of the isolation membrane: the isolation membrane is polyethylene (PE) with a thickness of 7 μm.
电解液的制备:在含水量小于10ppm的环境下,将LiPF 6加入非水有机溶剂,非水有机溶剂包括EC,PC和DEC,其中三种有机溶剂的质量比为:碳酸乙烯酯(EC):碳酸丙烯酯(PC):碳酸二乙酯(DEC)=2:2:6,LiPF 6的浓度为1.15mol/L,混合均匀,得到电解液。 Electrolyte preparation: In an environment with a water content of less than 10ppm, LiPF 6 is added to a non-aqueous organic solvent. The non-aqueous organic solvent includes EC, PC and DEC, and the mass ratio of the three organic solvents is: ethylene carbonate (EC) : Propylene Carbonate (PC): Diethyl Carbonate (DEC) = 2: 2: 6, the concentration of LiPF 6 is 1.15mol/L, mix well to obtain electrolyte solution.
锂离子电池的制备:将正极、隔离膜、负极按顺序依次叠好,使隔离膜处于正极和负极中间起到隔离的作用,并卷绕得到电极组件。将电极组件置于外包装铝塑膜中,在80℃下脱去水分后,注入上述电解液并封装,经过化成,脱气,切边等工艺流程得到锂离子电池。Preparation of lithium-ion battery: stack the positive electrode, separator, and negative electrode in order, so that the separator is in the middle of the positive electrode and the negative electrode to play the role of isolation, and wind up to obtain the electrode assembly. The electrode assembly is placed in the outer packaging aluminum-plastic film, after dehydration at 80°C, the above electrolyte is injected and packaged, and the lithium-ion battery is obtained through chemical formation, degassing, trimming and other processes.
铜箔6μm厚度,相比于一般的铜箔厚度8μm至16μm,意味着更小的电阻,与本申请中的硬碳材料结合,能实现大倍率充放电,并且具有更高的能量密度。The thickness of the copper foil is 6 μm, which means that the resistance is lower than that of the general copper foil, which is 8 μm to 16 μm. Combined with the hard carbon material in this application, it can achieve a large rate of charge and discharge, and has a higher energy density.
其他实施例和对比例是在实施例1的步骤的基础上进行参数变更,具体变更的参数如下面的表格所示。In other embodiments and comparative examples, parameters are changed on the basis of the steps in Example 1, and the specific changed parameters are shown in the table below.
下面描述本申请的各个参数的测试方法。The test method of each parameter of the present application is described below.
1)高低温性能的测试1) High and low temperature performance test
在25℃的环境中,将电池恒流放电至3V,进行第一次充电和放电,在0.7C的充电电流下进行恒流和恒压充电,直到上限电压为4.48V,然后在0.2C的放电电流下进行恒流放电,直到最终电压为3V,此时记录25℃的放电容量B;然后重复对电池进行0.7C的充电电流下恒流和恒压充电,直到上限电压为4.48V,调整温度为-20℃,然后在0.2C的放电电流下进行恒流放电,直到最终电压为3V,此时记录-20℃时的放电容量A。调整温度为25℃,在0.7C的充电电流下进行恒流和恒压充电,直到上限电压为4.48V,然后调整温度为45℃,在0.2C的放电电流下进行恒流放电,直到最终电压为3V,此时记录45℃时的放电容量C。In an environment of 25°C, discharge the battery at a constant current to 3V, charge and discharge for the first time, charge at a constant current and constant voltage at a charging current of 0.7C until the upper limit voltage is 4.48V, and then charge at a charging current of 0.2C Carry out constant current discharge under the discharge current until the final voltage is 3V. At this time, record the discharge capacity B at 25°C; then repeat the constant current and constant voltage charge at the charging current of 0.7C until the upper limit voltage is 4.48V, adjust The temperature is -20°C, and then a constant current discharge is performed at a discharge current of 0.2C until the final voltage is 3V, and the discharge capacity A at -20°C is recorded at this time. Adjust the temperature to 25°C, perform constant current and constant voltage charging at a charging current of 0.7C until the upper limit voltage is 4.48V, then adjust the temperature to 45°C, and perform constant current discharge at a discharging current of 0.2C until the final voltage It is 3V, and the discharge capacity C at 45°C is recorded at this time.
低温容量保持率A/B=(25℃的放电容量B/-20℃时的放电容量A)×100%Low temperature capacity retention rate A/B=(discharge capacity B at 25°C/discharge capacity A at -20°C)×100%
高温容量保持率C/B=(45℃的放电容量C/25℃时的放电容量B)×100%High temperature capacity retention C/B=(discharge capacity C at 45°C/discharge capacity B at 25°C)×100%
2)倍率性能的测试2) Test of rate performance
在25℃的环境中,将电池恒流放电至3V,进行第一次充电和放电,在0.7C的充电电流下进行恒流和恒压充电,直到上限电压为4.48V,然后在0.2C的放电电流下进行恒流放电,直到最终电压为3V,此时记录0.2C的放电容量,然后重复对电池进行0.7C的充电电流下恒流和恒压充电,直到上限电压为4.48V,依次设置放电倍率为1C和5C恒流放电,直到最终电压为3V,此时记录1C和5C的放电容量In an environment of 25°C, discharge the battery at a constant current to 3V, charge and discharge for the first time, charge at a constant current and constant voltage at a charging current of 0.7C until the upper limit voltage is 4.48V, and then charge at a charging current of 0.2C Carry out constant current discharge under the discharge current until the final voltage is 3V. At this time, record the discharge capacity of 0.2C, and then repeat the constant current and constant voltage charge of the battery at the charge current of 0.7C until the upper limit voltage is 4.48V, set in turn The discharge rate is 1C and 5C constant current discharge, until the final voltage is 3V, at this time record the discharge capacity of 1C and 5C
1C的容量保持率D/B=(0.2C的放电容量/1C时的放电容量)×100%1C capacity retention rate D/B=(0.2C discharge capacity/1C discharge capacity)×100%
5C的容量保持率E/B=(0.2C的放电容量/5C时的放电容量)×100%5C capacity retention E/B=(0.2C discharge capacity/5C discharge capacity)×100%
表1中实施例2至8与实施例1的区别为调整固化剂和环氧树脂的比例,使得环氧树脂和固化剂(间苯二胺)的质量比例分别处于1:1至10:1之间,并且,通过辊压的控制,从而实现材料微晶层间距为表1中所示,并且,得到合适的负极活性材料层的孔隙率。The difference between Examples 2 to 8 in Table 1 and Example 1 is to adjust the ratio of curing agent to epoxy resin so that the mass ratio of epoxy resin to curing agent (m-phenylenediamine) is 1:1 to 10:1 respectively Between, and, through the control of rolling pressure, so as to realize the interlayer spacing of material microcrystals as shown in Table 1, and obtain a suitable porosity of the negative electrode active material layer.
表1示出了实施例1至8和对比例1至2的各个参数和评估结果。Table 1 shows the respective parameters and evaluation results of Examples 1 to 8 and Comparative Examples 1 to 2.
Figure PCTCN2021101236-appb-000001
Figure PCTCN2021101236-appb-000001
Figure PCTCN2021101236-appb-000002
Figure PCTCN2021101236-appb-000002
注:H 1为0%荷电状态下电化学装置的负极厚度,H 2为50%荷电状态下电化学装置的负极厚度,H 3为100%荷电状态下电化学装置的负极厚度。 Note: H1 is the thickness of the negative electrode of the electrochemical device at 0% state of charge, H2 is the thickness of the negative electrode of the electrochemical device at 50% state of charge, and H3 is the thickness of the negative electrode of the electrochemical device at 100% state of charge.
请参考表1,对比表1中实施例1至实施例5可以看出,随着负极材料的微晶片层间距的增加,电化学装置的A/B的值升高,循环膨胀减小。可见负极材料的微晶片层间距对电化学装置的低温充电性能具有影响,在材料的微晶片层较小时,造成负极材料性能受损,主要的原因包括在低温条件下电解液离子传输变慢,在此基础上,较小的微晶片层间距加大了锂离子的传输阻力,导致负极材料的膨胀变大。可是负极微晶间距不宜大于0.4nm,因为当负极材料的微晶片层间距过大时,电解液中部分溶剂可能共嵌入负极材料,破坏负极材料的结构,影响电化学装置整体电性能。同时注意到C/B对材料的片层间距也相对敏感,低层间距引起嵌锂阻力增大的情况下,材料嵌锂动力学差,高温下容易在嵌锂过程产生结构破坏,因此对材料而言不利。对比例2由于低温下层间距过小,带来的阻抗和极化极大,引起低温性能的降低。Please refer to Table 1. Comparing Example 1 to Example 5 in Table 1, it can be seen that as the distance between the microchip layers of the negative electrode material increases, the A/B value of the electrochemical device increases and the cycle expansion decreases. It can be seen that the microchip layer spacing of the negative electrode material has an impact on the low-temperature charging performance of the electrochemical device. When the microchip layer of the material is small, the performance of the negative electrode material is damaged. The main reason includes the slow ion transport of the electrolyte under low temperature conditions. On this basis, the smaller interlayer spacing of microchips increases the transport resistance of lithium ions, resulting in larger expansion of the negative electrode material. However, the distance between the microcrystals of the negative electrode should not be greater than 0.4nm, because when the distance between the microchips of the negative electrode material is too large, some solvents in the electrolyte may be co-embedded in the negative electrode material, destroying the structure of the negative electrode material and affecting the overall electrical performance of the electrochemical device. At the same time, it is noticed that C/B is also relatively sensitive to the lamellar spacing of the material. When the intercalation resistance increases due to the low interlayer spacing, the lithium intercalation kinetics of the material is poor, and the structural damage is easy to occur during the lithium intercalation process at high temperature, so it is not good for the material. Bad words. In Comparative Example 2, due to the too small interlayer spacing at low temperature, the resulting impedance and polarization are extremely large, resulting in a decrease in low temperature performance.
对比表1中实施例6至实施例8可以看出,随着负极活性材料层的孔隙率的增大,电芯的A/B先增大,后减小。这是因为当孔隙率太小时,电解液浸润不足,低温下材料易析锂,随着孔隙率的增加,电解液与材料的接触更充分,嵌锂和脱锂的距离缩短,使得材料的动力学性能提升。但是在继续增大的过程中,对比例1相比于实施例1,虽然C/B有一定的提高,但是其低温性能较差。Comparing Examples 6 to 8 in Table 1, it can be seen that as the porosity of the negative electrode active material layer increases, the A/B of the cell first increases and then decreases. This is because when the porosity is too small, the infiltration of the electrolyte is insufficient, and the material is prone to lithium separation at low temperatures. With the increase of the porosity, the contact between the electrolyte and the material is more sufficient, and the distance between lithium intercalation and delithiation is shortened, making the power of the material Improve academic performance. However, in the process of continuing to increase, compared with Example 1, Comparative Example 1 has a certain improvement in C/B, but its low-temperature performance is poor.
表2中实施例9至实施例12,粘结力的变化由PAA(聚丙烯酸)粘接剂量的变化控制,控制PAA的比例为2.8%至6%,随着PAA比例的增加,活性材料与集流体之间的粘结力上升。实施例13至实施例15颗粒的破碎率由冷压时的辊压变化引起,其使用的辊压压力为30至50吨,对比例3至4使用的辊压大于等于60吨。Embodiment 9 to embodiment 12 in table 2, the change of cohesive force is controlled by the change of PAA (polyacrylic acid) adhesive quantity, and the ratio of controlling PAA is 2.8% to 6%, and along with the increase of PAA ratio, active material and The cohesive force between the current collectors increases. The crushing rate of the particles in Examples 13 to 15 is caused by the change of roll pressure during cold pressing, and the roll pressure used is 30 to 50 tons, and the roll pressure used in Comparative Examples 3 to 4 is greater than or equal to 60 tons.
表2示出了实施例4以及实施例9至15和对比例3至4的各个参数和评估结果。Table 2 shows the respective parameters and evaluation results of Example 4 and Examples 9 to 15 and Comparative Examples 3 to 4.
Figure PCTCN2021101236-appb-000003
Figure PCTCN2021101236-appb-000003
请参考表2,在实施例4的基础上调节粘结力,实施例9至实施例12随着负极活性材料层与负极集流体之间的粘结力的增加,颗粒破碎率维持较低水平时,电化学装置的低温容量保持率维持稳定水平,1C倍率和5C倍率下的容量保持率降低。这是因为,当负极活性材料层和负极集流体之间粘结力过大时,负极的粘结剂的含量过高,粘接剂未非导体,在阻碍锂离子的迁移的同时也降低导电子能力,极片内阻增加,影响负极材料的动力学性能,因此导致电化学装置的1C倍率和5C倍率下的容量保持率降低。但粘结力不能过小,如对比例3,过小时可能存在因为粘结力较小导致负极活性材料层与负极集流体剥离的情况,导致内阻增加和倍率性能下降。Please refer to Table 2, adjust the binding force on the basis of Example 4, and in Example 9 to Example 12, as the binding force between the negative electrode active material layer and the negative electrode current collector increases, the particle breakage rate maintains a low level , the low-temperature capacity retention rate of the electrochemical device maintained a stable level, and the capacity retention rate at 1C rate and 5C rate decreased. This is because, when the binding force between the negative electrode active material layer and the negative electrode current collector is too large, the content of the binder in the negative electrode is too high, and the binder is not a non-conductor, which also reduces the conductivity while hindering the migration of lithium ions. The increase of the electronic capacity and the internal resistance of the pole piece affects the kinetic performance of the negative electrode material, thus resulting in a decrease in the capacity retention rate of the electrochemical device at 1C rate and 5C rate. However, the binding force should not be too small. For example, in Comparative Example 3, if the binding force is too small, the negative electrode active material layer and the negative electrode current collector may peel off due to the small binding force, resulting in an increase in internal resistance and a decrease in rate performance.
请参考表2,在实施例4的基础上调节负极颗粒破碎率,实施例13至实施例15,调整颗粒随着负极材料的颗粒破碎率的增加,倍率性能受阻,由于破碎造成的颗粒间的电接触网络进一步影响,阻抗增加和SEI增厚进一步加重极化,易造成电流不均和析锂,并使颗粒脱离集流体,随着破碎率的增加1C倍率的容量保持率D/B和5C倍率下的容量保持率E/B减小。因此,负极材料的颗粒破碎率需控制在低于40%,对比例4拥有较高的破碎率,材料整体倍率性能很差。Please refer to Table 2, on the basis of Example 4, adjust the negative electrode particle breakage rate, embodiment 13 to embodiment 15, adjust the particle along with the increase of the particle breakage rate of the negative electrode material, the rate performance is hindered, due to the particle breakage caused by broken The further impact of the electrical contact network, the increase in impedance and the thickening of SEI will further aggravate the polarization, which will easily cause uneven current and lithium precipitation, and make the particles separate from the current collector. With the increase of the breakage rate, the capacity retention rate of 1C rate D/B and 5C The capacity retention ratio E/B at the rate decreases. Therefore, the particle breakage rate of the negative electrode material needs to be controlled below 40%. Comparative Example 4 has a relatively high breakage rate, and the overall rate performance of the material is very poor.
表3示出了实施例16至22的各个参数和评估结果。Table 3 shows the respective parameters and evaluation results of Examples 16 to 22.
Figure PCTCN2021101236-appb-000004
Figure PCTCN2021101236-appb-000004
Figure PCTCN2021101236-appb-000005
Figure PCTCN2021101236-appb-000005
请参考表3,实施例16至实施例19在实施例4的基础上调节调节CB值,可以看出,随着CB值的降低,电化学装置的低温容量保持率和1C,5C倍率下的容量保持率有一个先变化不大然后降低的过程,CB变化由0.95至0.9下降最快。这是因为实施例16至19的负极材料属于硬碳材料,硬碳材料具有一定的过嵌能力,因此在CB值为0.95时,依然可以正常工作,从而获得比较大的能量密度,但当CB值低于0.95时,由于正极提供的锂离子过多,导致负极材料析锂,且影响低温性能和倍率性能,当CB值超过1.1时,由于CB值过大,导致电化学装置的能量密度下降,且阳极电位抬升,迫使阴极电位抬升,不利于电性能发挥。Please refer to Table 3. Example 16 to Example 19 adjust and adjust the CB value on the basis of Example 4. It can be seen that as the CB value decreases, the low-temperature capacity retention rate of the electrochemical device and 1C, 5C rate The capacity retention rate has a process of first changing little and then decreasing, and the change of CB from 0.95 to 0.9 decreases the fastest. This is because the negative electrode materials in Examples 16 to 19 belong to hard carbon materials, and hard carbon materials have a certain over-intercalation ability, so when the CB value is 0.95, they can still work normally, thereby obtaining a relatively large energy density, but when the CB value is 0.95 When the value is lower than 0.95, due to the excessive lithium ions provided by the positive electrode, the negative electrode material will precipitate lithium, and affect the low-temperature performance and rate performance. When the CB value exceeds 1.1, the energy density of the electrochemical device will decrease due to the excessive CB value. , and the anode potential rises, forcing the cathode potential to rise, which is not conducive to the performance of electrical performance.
请参考表3,在实施例4的基础上调节M 1/M 2值,从实施例17至21可以看出,随着单位面积单面正极活性材料层的重量M 1与单位面积的负极活性材料层的重量M 2的比值的增加,电化学装置的低温容量保持率降低,1C倍率和5C倍率下的容量保持率也降低。这是因为随着M 1/M 2的增加,正极材料的动力学性能较差,将影响电化学整体的动力学性能,进而影响1C倍率和5C倍率下的容量保持率。因此设计时,需要根据负极材料和正极材料的容量等情况进行合理的匹配,使得电芯设计的M 1/M 2在优选范围内。 Please refer to Table 3, adjust the M 1 /M 2 value on the basis of Example 4, as can be seen from Examples 17 to 21, with the weight M 1 of the single-sided positive electrode active material layer per unit area and the negative electrode activity per unit area As the ratio of the weight M of the material layer increases, the low - temperature capacity retention rate of the electrochemical device decreases, and the capacity retention rate at 1C rate and 5C rate also decreases. This is because with the increase of M 1 /M 2 , the kinetic performance of the cathode material is poor, which will affect the overall electrochemical kinetic performance, and then affect the capacity retention at 1C rate and 5C rate. Therefore, when designing, it is necessary to make a reasonable match according to the capacity of the negative electrode material and the positive electrode material, so that the M 1 /M 2 of the cell design is within the preferred range.
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明。本领域技术人员应当理解,本申请中所涉及的公开范围,并不限于上述技术特征的特定组合而成的技术方案,同时也应涵盖由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的具有类似功能的技术特征进行互相替换而形成的技术方案。The above description is only a preferred embodiment of the present application and an illustration of the applied technical principles. Those skilled in the art should understand that the scope of disclosure involved in this application is not limited to technical solutions formed by a specific combination of the above technical features, but also covers other technical solutions formed by any combination of the above technical features or their equivalent features. Technical solutions. For example, a technical solution formed by replacing the above-mentioned features with technical features with similar functions disclosed in this application.

Claims (10)

  1. 一种电化学装置,其特征在于,An electrochemical device, characterized in that,
    所述电化学装置在-20℃的0.2C放电容量为A,所述电化学装置在25℃的0.2C放电容量为B,且70%≤A/B≤90%。The 0.2C discharge capacity of the electrochemical device at -20°C is A, the 0.2C discharge capacity of the electrochemical device at 25°C is B, and 70%≤A/B≤90%.
  2. 根据权利要求1所述的电化学装置,其特征在于,所述电化学装置在45℃的0.2C放电容量为C,103%≤C/B≤110%。The electrochemical device according to claim 1, characterized in that the 0.2C discharge capacity of the electrochemical device at 45°C is C, 103%≤C/B≤110%.
  3. 根据权利要求1所述的电化学装置,其特征在于,满足如下(a)或(b)中的至少一者:The electrochemical device according to claim 1, wherein at least one of the following (a) or (b) is satisfied:
    (a)所述电化学装置包括负极,所述电化学装置在50%荷电状态时,所述负极的厚度为H 2,所述电化学装置在0%荷电状态时,所述负极的厚度为H 1,(H 2-H 1)/H 1为0%至6%; (a) The electrochemical device includes a negative electrode. When the electrochemical device is at a state of charge of 50%, the thickness of the negative electrode is H2 . When the electrochemical device is at a state of charge of 0%, the thickness of the negative electrode is The thickness is H 1 , (H 2 -H 1 )/H 1 is 0% to 6%;
    (b)所述电化学装置包括负极,所述电化学装置在100%荷电状态时,所述负极的厚度为H 3,所述电化学装置在0%荷电状态时,所述负极的厚度为H 1,(H 3-H 1)/H 1为0%至8%。 (b) The electrochemical device includes a negative electrode. When the electrochemical device is in a state of charge of 100%, the thickness of the negative electrode is H 3 . When the electrochemical device is in a state of charge of 0%, the thickness of the negative electrode is The thickness is H 1 , and (H 3 -H 1 )/H 1 is 0% to 8%.
  4. 根据权利要求1所述的电化学装置,其特征在于,所述电化学装置包括负极,所述负极包括负极集流体和位于所述负极集流体的负极活性材料层,所述负极活性材料层的孔隙率为20%至50%。The electrochemical device according to claim 1, wherein the electrochemical device comprises a negative electrode, the negative electrode includes a negative electrode current collector and a negative electrode active material layer located on the negative electrode current collector, and the negative electrode active material layer of the negative electrode active material layer The porosity is 20% to 50%.
  5. 根据权利要求1所述的电化学装置,其特征在于,所述电化学装置包括负极,所述负极包括负极集流体和位于所述负极集流体的负极活性材料层,所述负极活性材料层包括负极材料,所述负极材料包括硬碳,且满足如下(c)至(g)中的至少一者:The electrochemical device according to claim 1, wherein the electrochemical device comprises a negative electrode, the negative electrode comprises a negative electrode current collector and a negative electrode active material layer located on the negative electrode current collector, and the negative electrode active material layer comprises Negative electrode material, the negative electrode material includes hard carbon, and satisfies at least one of the following (c) to (g):
    (c)所述负极活性材料层与所述负极集流体之间的粘结力为10N/m至50N/m;(c) the bonding force between the negative electrode active material layer and the negative electrode current collector is 10N/m to 50N/m;
    (d)所述负极活性材料层的压实密度为0.9g/cm 3至1.25g/cm 3(d) the compacted density of the negative electrode active material layer is 0.9g/cm 3 to 1.25g/cm 3 ;
    (e)所述负极材料的颗粒破碎率为10%至40%;(e) the particle breakage rate of the negative electrode material is 10% to 40%;
    (f)所述负极材料的X射线衍射图谱中,在18°至30°之间具有一个衍射峰,所述衍射峰的半高峰宽为4°至10°;(f) In the X-ray diffraction pattern of the negative electrode material, there is a diffraction peak between 18° and 30°, and the half-height width of the diffraction peak is 4° to 10°;
    (g)所述负极材料的微晶片层间距为0.34nm至0.4nm。(g) The microchip layer spacing of the negative electrode material is 0.34nm to 0.4nm.
  6. 根据权利要求1所述的电化学装置,其特征在于,满足如下(h)或(i)的至少一项:The electrochemical device according to claim 1, wherein at least one of the following (h) or (i) is satisfied:
    (h)所述电化学装置在25℃的1C放电容量为D,0.9<D/B<1;(h) The 1C discharge capacity of the electrochemical device at 25°C is D, 0.9<D/B<1;
    (i)所述电化学装置在25℃的5C放电容量为E,99%≤E/B≤105%。(i) The 5C discharge capacity of the electrochemical device at 25°C is E, 99%≤E/B≤105%.
  7. 根据权利要求1所述的电化学装置,其特征在于,对所述电化学装置进行三电极电位监控,在以电压为纵坐标,荷电状态为横坐标作图,负极脱锂曲线在0.3V至0.8V为斜坡区,负极脱锂曲线在0.2V以下的荷电状态占比F为30%至80%。The electrochemical device according to claim 1, wherein the three-electrode potential is monitored on the electrochemical device, and the voltage is taken as the ordinate, and the state of charge is used as the abscissa to draw a graph, and the negative electrode delithiation curve is at 0.3V From 0.8V to 0.8V is the slope area, and the charge state ratio F of the negative electrode delithiation curve below 0.2V is 30% to 80%.
  8. 根据权利要求1所述的电化学装置,其特征在于,所述电化学装置包括正极和负极,所述正极包括正极集流体和位于所述正极流体上的正极活性材料层,所述负极包括负极集流体和位于所述负极集流体上的负极活性材料层,单位面积的单面所述正极活性材料层的重量为M 1,单位面积的单面所述负极活性材料层的重量为M 2,M 1/M 2为2至6。 The electrochemical device according to claim 1, wherein the electrochemical device comprises a positive electrode and a negative electrode, the positive electrode includes a positive electrode current collector and a positive electrode active material layer on the positive electrode fluid, and the negative electrode includes a negative electrode The current collector and the negative active material layer positioned on the negative current collector, the weight of the positive active material layer on one side per unit area is M 1 , and the weight of the negative active material layer on one side per unit area is M 2 , M 1 /M 2 is 2 to 6.
  9. 根据权利要求1所述的电化学装置,其特征在于,所述电化学装置的CB值为0.9至1.1;The electrochemical device according to claim 1, wherein the CB value of the electrochemical device is 0.9 to 1.1;
    其中,CB=负极容量/正极容量,所述负极容量=CW 负极×克容量 负极×活性材料百分含量 负极,所述正极容量=CW 正极×克容量 正极×活性材料百分含量 正极Wherein, CB=negative electrode capacity/positive electrode capacity, said negative electrode capacity=CW negative electrode ×gram capacity negative electrode ×active material percentage content negative electrode , said positive electrode capacity=CW positive electrode ×gram capacity positive electrode ×active material percentage content positive electrode .
  10. 一种电子装置,其特征在于,包括权利要求1至9中任一项所述的电化学装置。An electronic device, characterized by comprising the electrochemical device according to any one of claims 1-9.
PCT/CN2021/101236 2021-06-21 2021-06-21 Electrochemical device and electronic device WO2022266799A1 (en)

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