WO2022033375A1 - 复合正极材料、正极极片及其制作方法、电池 - Google Patents
复合正极材料、正极极片及其制作方法、电池 Download PDFInfo
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- WO2022033375A1 WO2022033375A1 PCT/CN2021/110587 CN2021110587W WO2022033375A1 WO 2022033375 A1 WO2022033375 A1 WO 2022033375A1 CN 2021110587 W CN2021110587 W CN 2021110587W WO 2022033375 A1 WO2022033375 A1 WO 2022033375A1
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- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to the technical field of batteries, in particular to a composite positive electrode material, a positive electrode sheet, a method for making the same, and a battery.
- ternary materials Due to its high energy density, ternary materials are widely used as cathode materials for electric vehicle batteries. At the same time, with the continuous improvement of energy density requirements for electric vehicles, the ternary materials used are also composed of LiNi 1/3 Co 1/3 Mn 1/3 O 2 is transformed into LiNi 0.5 Co 0.2 Mn 0.3 O 2 , and even many ternary material companies have begun to develop LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.8 Co 0.1 Mn 0.1 O 2 , LiNiO 2 , NCA, etc. Nickel material.
- ternary high-nickel materials have problems such as poor cycle performance at room temperature, increased DCIR (direct current resistance at a specific load and discharge current) after cycling, severe gas production after cycling, and poor safety performance.
- the current technical solution is to use the optimization of coating, doping and sintering processes to improve the structural stability of the material as much as possible, and to slow down the phase transformation of the material during long-term cycling. Capacity fading, improving material safety.
- This technical solution cannot essentially solve the phase transition change of the material in a fixed charge-discharge interval, but only improves the structural stability of the material.
- one aspect of the present invention provides a composite positive electrode material, which includes: a ternary material and a phase change material, the phase change material has a phase change platform in the charge-discharge interval of the ternary material, and the ternary material is a single crystal structure, the phase change material is a single crystal structure or an agglomerate structure, and the phase change material is coated on the surface of the ternary material; the mass fraction ratio of the ternary material to the phase change material is 80:20-99.8:0.2; the nanohardness of the ternary material is 0.001-5Gpa, the nanohardness of the phase change material is 0.01-10GPa; the D50 of the ternary material is 3.0-6.0 ⁇ m, the phase The primary particle D50 of the variable material is 10-50 nm.
- the nanohardness of the ternary material is 0.2-1.4GPa, and the nanohardness of the phase change material is 1.5-3.5GPa.
- the tap density of the ternary material is 2.0-2.8 g/cm 3
- the tap density of the phase change material is 0.8-1.5 g/cm 3 .
- the D50 of the ternary material is 3.5-5.0 ⁇ m, and the particle size D50 of the primary particles of the phase change material is 20-40 nm.
- the ternary material includes a nickel-cobalt-manganese ternary material or a nickel-cobalt-aluminum ternary material.
- the phase change material has an olivine structure
- the phase change material includes lithium iron manganese phosphate, lithium manganese vanadium phosphate or lithium iron chrome phosphate.
- Another aspect of the present invention provides a method for making the composite positive electrode material according to the present invention, which comprises: charging a certain mass ratio of ternary material, phase change material and NMP solvent into a mechanical fusion machine for fusion to form a composite material material; bake the fused composite material at a certain temperature to obtain the composite positive electrode material, wherein the ternary material is a single crystal material, and the particle size D50 of the ternary material is 3.0- 6.0 ⁇ m, the phase change material is a single crystal material or a secondary spherical material, the particle size D50 of the primary particles of the phase change material is 10-50 nm, and the mass fraction ratio of the ternary material to the phase change material is 80:20-99.8-0.2, the nano-hardness of the ternary material is 0.001-5 GPa, and the nano-hardness of the phase change material is 0.01-10 GPa.
- the rotational speed of the mechanical fusion machine is 4000-7000 r/min, and the fusion time is 10-30 min.
- the rotational speed of the mechanical fusion machine is 4500-6500 r/min, and the fusion time is 15-25 min.
- the baking temperature of the composite material is 80-120° C.
- the baking time is 0.5-2.5 h.
- the baking temperature of the composite material is 95-105° C.
- the baking time is 1-2 h.
- Another aspect of the present invention provides a positive electrode sheet, which includes a current collector and the composite positive electrode material according to the present invention disposed on the current collector.
- the strength ratio of the crystal orientation 003/110 after the positive pole piece is pressed is 10-100.
- Another aspect of the present invention provides a method for making a positive electrode plate according to the present invention, which includes: adding a certain amount of NMP solvent to PVDF to form a PVDF solution, the polymer chain of the PVDF has F-containing group and/or carboxyl group, ester group, amino group; in the PVDF solution, add a certain amount of conductive agent material, and stir to form a slurry; after a certain period of time, add the method according to the present invention to the slurry
- the composite positive electrode material is fully stirred to obtain the final slurry; the final slurry is coated on the current collector, and then the NMP solvent in the slurry is removed by high temperature baking, and the positive electrode is obtained by rolling and slicing pole piece.
- the method before obtaining the final slurry, the method further includes: adding a certain amount of lithium carbonate to the slurry.
- a battery which includes a positive electrode piece according to the present invention, a negative electrode piece, and a separator disposed between the positive electrode piece and the negative electrode piece.
- the composite positive electrode material, the positive electrode sheet and the manufacturing method thereof, and the battery proposed by the present invention since the positive electrode material includes a ternary single crystal material and a phase change material coated on the surface of the ternary single crystal material, on the one hand, the ternary single crystal material
- the material itself has the advantages of good high temperature performance, less gas production and high safety.
- the heat release of the ternary material improves the safety; and the phase change of the ternary material in the charge-discharge interval is slowed down or delayed by the phase change material, and the capacity decay caused by the phase change of the ternary material during the long-term cycle is slowed down, thereby improving
- the cycle performance of the battery reduces the resistance increase of the material during the aging process and improves the safety of the battery.
- the orientation orientation of the ternary material in the 003 crystal direction is limited by defining the nanohardness of the ternary material and the phase change material, and the tap density of the ternary material and the phase change material is limited. High compaction of the pole piece is achieved to ensure the energy density of the battery.
- FIG. 1 shows a schematic structural diagram of a composite cathode material according to an embodiment of the present invention
- Fig. 3 shows a partial enlarged view of the CV graph shown in Fig. 2;
- FIG. 4 shows the orientation of the ternary single crystal material and the composite cathode material according to the embodiment of the present invention in the crystal direction 003;
- Fig. 5 shows the XRD pattern of conventional ternary material and the composite positive electrode material according to the embodiment of the present invention after the pole piece is pressed;
- Figure 6 shows a schematic flow diagram of a method for making a composite cathode material according to the present invention
- Figure 7 shows a schematic flow diagram of a method for making a positive pole piece according to the present invention.
- Spatial relational terms such as “under”, “below”, “below”, “under”, “above”, “above”, etc., may be used herein for convenience of description This describes the relationship of one element or feature shown in the figures to other elements or features. It should be understood that the spatially relative terms are intended to encompass different orientations of the device in use and operation in addition to the orientation shown in the figures. For example, if the device in the figures is turned over, then elements or features described as “below” or “beneath” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the exemplary terms “below” and “under” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatial descriptors used herein interpreted accordingly.
- ternary high-nickel materials have problems such as poor cycle performance at room temperature, increased DCIR (direct current resistance at a specific load and discharge current) after cycling, serious gas production after cycling, and poor safety performance.
- the current technical solution is to use the optimization of coating, doping and sintering processes to improve the structural stability of the material as much as possible, and to slow down the phase change of the material during long-term cycling. Capacity fading, improving material safety.
- this technical solution cannot essentially solve the phase change change of the material in a fixed charge-discharge interval, but only improves its structural stability from the aspect of the material.
- the recycling and safety performance of materials can be improved to overcome the current problems.
- the idea of the invention is to coat a phase change material on the surface of the ternary material on the basis of improving the structural stability of the bulk material, so as to improve the cycle and safety performance of the ternary material.
- the general idea is to use the charging and discharging characteristics of different materials to share more charging and discharging tasks on the charging and discharging platform of high nickel materials at about 4.25V (relative to the potential of Li), and slow down or delay the charging and discharging of materials.
- the phase change in the interval; at the same time, the phase change material is uniformly coated on the surface of the ternary material, and the coating layer acts as a thermal barrier, thereby increasing the onset temperature of the material's thermal runaway and reducing the release of the material during thermal runaway. heat.
- the composite cathode material proposed by the present invention includes a ternary material 11 and a phase change material 12 , and the phase change material 12 has a phase change platform in the charge and discharge range of the ternary material, so that the Slowing down or delaying the phase transition of the ternary material in the charge-discharge interval, slowing down the capacity decay caused by the phase transition of the ternary material in the long-term cycle process, thereby improving the cycle performance of the battery and reducing the resistance increase of the material during the aging process , improve the safety of the battery.
- the mass ratio of the ternary material and the phase change material is 80:20-99.8-0.2, and as an example, the mass ratio of the ternary material and the phase change material is 90:10 to 95:5.
- the ternary material includes a nickel cobalt manganese ternary material (ie, NCM) or a nickel cobalt aluminum ternary material (ie, NCA).
- the ternary material is a high nickel ternary material, and x in LiNi x Co y M z+ is greater than 0.6.
- the phase change material includes lithium iron manganese phosphate, lithium manganese vanadium phosphate, or lithium iron chromium phosphate.
- the phase change material is lithium manganese iron phosphate (LMFP), and its structure is LiMn x Fe y PO 4 , wherein the value range of x is 0.05-0.95, preferably 0.5-0.85; the value range of y is is 0.05-0.95, preferably in the range of 0.15-0.5; the material is a single crystal material.
- the material is a single crystal material.
- the phase change material has a phase change platform between 4.0-2.0V.
- the phase change material and the high-nickel material are formed into a composite positive electrode material, the high-nickel material can be weakened or delayed at 4.25V (relative to Li potential) structural phase transition.
- the ternary material is NCM811, and the composite material is a ternary material coated with LMFP.
- the CV curves of the battery pole pieces made by them are shown in Figures 2 and 3, of which Figure 3 is a partial enlarged view of Figure 2.
- the curve 1 represents the CV curve of NCM811, and the curve 2 represents the CV curve of the composite cathode material.
- the CV curve of the pole piece made of composite cathode material has a new oxidation peak near 4.15V, and at the same time reduces the current intensity of the oxidation peak of NCM811 material at about 4.25V, which indicates that the composite material must be Materials with a phase transition platform between 4.0-2.0V, such as 3.95-4.15V (such as lithium manganese iron phosphate, lithium manganese vanadium phosphate, lithium iron chrome phosphate, etc.) can weaken or delay high nickel materials at 4.25. Structural phase transition of V (potential with respect to Li).
- the ternary material is a single crystal material
- the composite material is a layer of phase change material, such as LMFP, on the surface of the single crystal ternary material.
- the ternary single crystal material itself has the advantages of good high temperature performance, less gas production, and high safety. , thereby increasing the initial temperature of the material thermal runaway and reducing the heat released during the thermal runaway process, thereby improving the safety performance of the material.
- the ternary material adopts single crystal material
- the single crystal ternary material has the characteristics of crystal direction (003) orientation after the pole piece is pressed, as shown in Figure 4, this orientation will cause the thickness of the material to increase.
- the expansion of the direction affects the performance of the battery, causing uneven distribution of the electrolyte during the charging and discharging process of the battery, resulting in lithium precipitation and deterioration of the battery performance.
- the coating layer can effectively prevent the orientation of the ternary in the (003) crystal direction, reduce the expansion of the ternary material and the pole piece in the thickness direction, and improve the battery performance.
- the nanohardness of the ternary material and the coating material is limited.
- the nano-hardness of the element material is 0.001-5 GPa, and the nano-hardness of the coating material is 0.01-10 GPa.
- the nano-hardness of the ternary material is 0.2-1.4 GPa, and the nano-hardness of the coating material is 1.5-3.5 GPa.
- FIG. 5 shows XRD patterns of conventional ternary materials and composite cathode materials according to an embodiment of the present invention after the pole pieces are pressed.
- the curve 3 represents the XRD pattern of the conventional ternary material after the pole piece is pressed
- the curve 4 represents the XRD pattern of the composite positive electrode material according to the embodiment of the present invention after the pole piece is pressed, as shown in FIG.
- the intensity ratio of 003/110 of the XRD of the composite cathode material after the pole piece pressing is lower than the intensity ratio of 003/110 of the XRD after the pole piece pressing of the conventional ternary material, which indicates that the ternary single crystal material
- the directional orientation at 003 is suppressed.
- the intensity ratio of 003/110 of XRD of the conventional ternary material after the pole piece is pressed is in the range of 5-200, while the pole piece of the composite positive electrode material according to the embodiment of the present invention has a
- the 003/110 intensity ratio of the XRD after tablet compression was in the range of 10-100.
- the cladding material is a material such as LMFP
- the compaction of LMFP is low
- the energy density of the battery is affected.
- the solid density is limited, so that higher compaction of the pole pieces can be achieved to ensure the energy density of the battery.
- the tap density of the ternary material is 2.0-2.8 g/cm 3
- the tap density of the coating material is 0.8-1.5 g/cm 3 .
- the coating material adopts a material whose primary particles are nanoscale, and the D50 of the ternary material is 3.0-6.0 ⁇ m, The particle size D50 of the primary particles of the coating material is 10-50 nm.
- lithium carbonate in order to provide the safety performance of the material and the battery, a certain amount of lithium carbonate can be added to the slurry of the composite positive electrode material. Since lithium carbonate can produce gas when the battery fails, the CID and The reversal and opening time of the explosion-proof valve is advanced to prevent the occurrence of more serious thermal runaway.
- the content of lithium carbonate is 2-10%.
- the ternary single crystal material since the ternary single crystal material is used, and the surface of the ternary single crystal material is coated, on the one hand, the ternary single crystal material itself has good high temperature performance, less gas production, and safety. On the other hand, because the coating material acts as a thermal barrier on the surface of the ternary material, it can improve the thermal runaway initial temperature of the ternary material and the battery and the heat release during thermal runaway, which improves the safety.
- the orientation of the ternary material in the 003 crystal direction is limited by defining the nanohardness of the ternary material and the cladding material, and the tap density of the ternary material and the cladding material is limited. High compaction of the pole piece is achieved to ensure the energy density of the battery.
- Another aspect of the present invention provides a method for making the composite positive electrode material according to the present invention, as shown in FIG. 6 , which includes the following steps:
- Step 101 Load a certain mass ratio of ternary material, phase change material and NMP solvent into a mechanical fusion machine for fusion to form a composite material.
- the ternary material is a single crystal material
- the particle size D50 of the ternary material is 3.0-6.0 ⁇ m
- the phase change material is a single crystal material or a secondary spherical material
- the particle size D50 of the primary particles of the phase change material is 10-50 nm
- the mass fraction ratio of the ternary material to the phase change material is 80:20-99.8:0.2
- the nanohardness of the ternary material is 0.001-5Gpa
- the nanohardness of the phase change material is 0.01-10GPa.
- the ternary material and the phase change material can be prepared by methods commonly used in the art.
- the ternary material adopts NCM
- the phase change material adopts LMFP.
- the preparation methods thereof are, for example:
- the ternary material is obtained by mixing the ternary material precursor ( Nix Co y M z (OH) 2 ) and the lithium source and performing pre-sintering, first sintering, first crushing, second sintering and second crushing;
- the lithium source is one or more of lithium hydroxide, lithium carbonate, lithium nitrate and lithium acetate;
- the sintering temperature is 200-500°C
- the sintering time is 4-6h.
- the first sintering includes a constant temperature section, a heating section and a cooling section; the temperature of the first constant temperature section of the constant temperature section is 800-1000°C, the time of the first constant temperature section is 5-8h; the temperature of the second constant temperature section is 1000-1100°C , the time of the second constant temperature section is 8-10h; the temperature of the third constant temperature section is 1100-1200°C, and the time of the third constant temperature section is 5-10h;
- the temperature of the first heating section is 200-800°C, and the heating time of the first heating section is 1.5-3.5h; the temperature of the second heating section is 800-1000°C, and the heating time of the second heating section is 1.5-3.5h;
- the temperature of the third heating section is 1000-1200°C, and the heating time of the third heating section is 1.0-2.5h;
- the temperature of the first cooling section of the cooling section is 1200-800°C, and the cooling time of the first cooling section is 1.5-3h; the temperature of the second cooling section is 800-200°C, and the cooling time of the second cooling section is 0.5-2h .
- the key parameters of the first crushing are subjected to the first ball milling to form preliminary crushing, the rotation speed of the first ball milling is 4000-8000r/min, preferably 5500-7500r/min, and the first air crushing pressure is 5-10MPa, preferably is 6.5-8.5MPa.
- the coating agent contains Ti 3 O 4 , Mg(OH) 2 , W 2 O 3 , Al 2 O 3 , Co(OH) 2 and H 3 One or more of the BO 3 elements.
- the temperature of the second sintering is 500-800°C, preferably 550-750°C.
- the key parameters of the second crushing the second crushing adopts a mechanical mill, and the rotational speed of the mechanical mill is 2000-4000 r/min, preferably 2500-3500 r/min.
- the above process obtains a ternary positive electrode material.
- a certain proportion of FePO 4 , Li 2 CO 3 , glucose and water are mixed, and the mixed materials are processed by coarse grinding and fine grinding to form an aqueous solution; the aqueous solution is spray-dried to form a mixture of the three materials; under a certain high temperature Solid-phase sintering is performed, and the sintered material is gas-crushed to obtain an LMFP material.
- the rotational speed of the mechanical fusion machine is 4000-7000 r/min, and the fusion time is 10-30 min.
- the rotational speed of the mechanical fusion machine is 4500-6500 r/min, and the fusion time is 15-25 min.
- Step 102 baking the fused composite material at a certain temperature to obtain a composite positive electrode material.
- the baking temperature of the composite material is 80-120° C., and the baking time is 0.5-2.5 h.
- the baking temperature of the composite material is 95-105° C., and the baking time is 1-2 h.
- Another aspect of the present invention also provides a positive electrode sheet for a battery, which includes a current collector and a composite positive electrode material according to an embodiment of the present invention disposed on the current collector.
- the current collector is, for example, an aluminum foil.
- the strength ratio of the crystal orientation 003/110 after the positive electrode sheet is pressed is 10-100.
- the positive electrode sheet according to the present invention adopts the composite positive electrode material according to the embodiment of the present invention, it has similar advantages, that is, the cycle performance of the battery can be improved, the resistance increase of the material during the aging process can be reduced, and the safety of the battery can be improved.
- Another aspect of the present invention also provides a battery, which includes a positive pole piece according to an embodiment of the present invention, a negative pole piece, and a separator and an electrolyte disposed between the positive pole piece and the negative pole piece.
- the positive electrode sheet includes a current collector and a composite positive electrode material according to an embodiment of the present invention disposed on the current collector.
- the positive electrode current collector includes an aluminum foil. It should be understood that the positive electrode current collector is further provided with a conductive agent and a binder. As an example, the mass ratio of the composite positive electrode material: the binder: the conductive agent is 100:2.0:2.2.
- the composite cathode material is a single-crystal NCM coated with a layer of LMFP material whose primary particles are nanoscale, and the binder is PVDF (polyvinylidene fluoride) with special functional groups on the polymer chain.
- the functional group is the addition of an F-containing group, or a carboxyl group, an ester group or an amino group to the polymer chain.
- the addition of an F-containing group can increase the gel resistance, and the addition of a carboxyl group, an ester group or an amino group can improve the adhesion;
- the combination of conductive agents of carbon black, CNTs with different diameters, and graphene, these conductive agents can achieve mutual conduction at point-to-point, point-to-line, and line-to-line, which can better form a complete conductive network, because The two materials belong to nanoscale and microscale, and need point-like, wire-like or even planar conductive agents to form a complete conductive network.
- the negative electrode sheet includes a current collector and a negative electrode material disposed on the current collector.
- the negative electrode current collector includes a copper foil
- the negative electrode material is graphite.
- the mass ratio of graphite:binder:CMC:conducting agent is 100:1.9:1.6:1.2.
- the secondary particle carbon-coated artificial graphite used in the negative electrode graphite is because the primary particles are made of smaller secondary particles, and then in order to improve the conductivity, carbon is coated on the surface; it can improve the rate, low temperature performance, At the same time, the inherent expansion of graphite itself is reduced.
- the electrolyte includes one or more of EC, DMC, EMC, DEC, VC, PS, wherein EC, ethylene carbonate, Ethylene carbonate; DMC, dimethyl carbonate, Dimethyl carbonate; EMC , Ethyl Methyl Carbonate, Ethyl Methyl Carbonate; DEC, Diethyl Carbonate, Diethyl Carbonate; VC, Vinylene Carbonate, Vinylene Carbonate; PS, Polystyrene, Polystyrene.
- EC ethylene carbonate, Ethylene carbonate
- DMC dimethyl carbonate, Dimethyl carbonate
- EMC Ethyl Methyl Carbonate, Ethyl Methyl Carbonate
- DEC Diethyl Carbonate, Diethyl Carbonate
- VC Vinylene Carbonate, Vinylene Carbonate
- PS Polystyrene, Polystyrene.
- the separator adopts a composite structure composed of PE, ceramics, and glue.
- the battery according to the embodiment of the present invention adopts the composite cathode material according to the embodiment of the present invention, it has similar advantages, that is, the cycle performance of the battery can be improved, the resistance increase of the material during the aging process can be reduced, and the safety of the battery can be improved.
- Another aspect of the present invention also proposes a method for making a positive pole piece according to an embodiment of the present invention, which includes the following steps:
- Step 201 adding PVDF to a certain amount of NMP solvent to form a PVDF solution, that is, dissolving PVDF.
- PVDF adopts PVDF specially used for high nickel materials.
- the polymer chain of the PVDF has F-containing groups and carboxyl groups, ester groups or amino groups, so that PVDF has anti-gelling properties.
- the NMP Choinese name: NMP
- NMP Methylpyrrolidone
- Step 202 adding a certain amount of conductive agent material to the PVDF solution, and stirring to form a slurry.
- a vacuum high-speed batching equipment such as a vacuum-type high-speed planetary disperser to form a slurry.
- the stirring time is, for example, 10-50 minutes.
- the conductive agent material is a conductive agent combination of conductive carbon black, CNTs with different tube diameters, and graphene.
- Step 203 after a certain period of time, add the composite positive electrode material according to the present invention to the slurry, and perform sufficient stirring to obtain a final slurry.
- the composite positive electrode material is added to the slurry for thorough stirring to obtain the final slurry.
- the composite positive electrode material is as described above and will not be repeated here.
- step 204 the final slurry is coated on the current collector, and then the NMP solvent in the slurry is removed by baking at a high temperature, and the positive pole piece is obtained by rolling and slicing.
- the method further includes: adding a certain amount of lithium carbonate to the slurry to improve the safety performance of the battery and the material.
- the present invention also conducts experimental tests on the positive electrode piece prepared by the above method and the battery using the positive electrode piece to verify the performance of the battery.
- the agent is PVDF with special functional groups on the polymer chain; the conductive agent is a combination of conductive carbon black, CNTs with different diameters, and graphene.
- the electrolyte adopts the mixed solution of EC, DMC, EMC, DEC, VC and PS.
- the diaphragm is made of PE+ceramic+glue.
- composition and weight percentage of the slurry described in this experiment are as follows: PVDF5130: 2.1%; conductive agent 1.9%; composite cathode material (Ni83 surface is coated with a layer of LMFP material with nano-scale primary particles) 96%; the production process is as follows Dissolve PVDF; add different types of conductive agent materials; add composite cathode materials. Among them, the ratio of composite cathode material, PVDF and conductive agent in the slurry is 96:2.1:1.9.
- Table 1 is the experimental parameters and performance parameters of the embodiment
- Table 2 shows the experimental parameters and performance parameters of the comparative example
- Crystal orientation (003)/(110) after the pole piece is pressed the intensity ratio of XRD 003/110 after the pole piece is made of uncoated positive electrode material is in the range of 5-200; the composite positive electrode material coated with ternary material is made The intensity ratio of 003/110 after the pole piece ranges from 10-100.
- Pole piece compaction The pole piece of ternary material is generally compacted above 3.0g/cm 3 . Due to process limitations and the possibility that the material will be crushed, the compaction will generally not exceed 3.8g/cm 3 ;
- 45°C-C500 This refers to the capacity retention rate of the battery. The highest range in this range is no attenuation, which is 100%; there is also the phenomenon of battery cycle diving, and the capacity retention rate is very low, below 50%;
- battery thickness change rate/% This is mainly to evaluate the gas production of the battery. The best change rate is that the battery does not produce gas, and the change rate is 0; if the battery gas production is large, it can exceed 100%;
- Rate (C/0.2C discharge ratio): This is to evaluate the high current discharge capacity of the battery, and this value is generally 50%-98%;
- Low temperature (-20°C/25°C discharge ratio): This is to evaluate the low temperature discharge capability of the battery. This value fluctuates greatly depending on the battery, and can be 5%-90%.
- Test equipment laser particle size analyzer, reference model Malvern 2000/3000;
- Test method deionized water dispersion, ultrasonic for 10min; particle refractive index 1.74; volume distribution data such as D0.01, D10, D50, D90, D99 and original data need to be given.
- Vibration use Dandong Baxter (BT-1001) intelligent powder comprehensive tester to test, place the powder in a 100ml measuring cylinder and weigh; place the measuring cylinder on the tester to vibrate, and the number of vibrations is 300 times.
- the vibration frequency is 300 times/min; after the vibration is over, the volume of the powder in the measuring cylinder is tested. Calculate the tap density based on the weight and volume of the powder.
- Nano-hardness is tested by a nano-indenter, which continuously changes the load under computer control and monitors the indentation depth online.
- a complete indentation process consists of two steps, the so-called loading process and unloading process.
- an external load is applied to the indenter to press it into the surface of the sample.
- the depth of the indenter into the sample increases.
- the external load is removed and the sample There will be residual indentation marks on the surface.
- Nanohardness was calculated from the applied pressure and the area of the indentation. The nanohardness is related to the selected crystal plane.
- Pole piece compaction Take the unpressed positive pole piece, make it into a size of 40*100mm, use the Ono tablet press to press, and calculate the pole piece compaction according to the surface density of the pole piece and the thickness of the pole piece after pressing.
- Test method Temperature condition: 45 ⁇ 5°C; Charge: 1C constant current charge to 4.2V; Discharge: 1C constant current discharge to 2.5V; after 500 cycles, the discharge capacity of the first cycle is C1 As a reference, the capacity retention rate, which is C500, is calculated.
- the battery thickness change rate/% the battery is charged to 4.2V according to 0.2C constant current, placed at room temperature for 2h, and the initial thickness of the battery is recorded; the battery is stored in a constant temperature cabinet at 60°C for 28D, and the thickness after storage is recorded. , to calculate the thickness change.
- Rate at 25°C, charge: 0.2C constant current charge to 4.2V; discharge: 0.2C, 5C constant current discharge to 2.5V at different rates.
- the composite positive electrode materials in Examples 1-14 all have relatively excellent performance. Specifically, in terms of the orientation of the pressed sheet after the composite positive electrode material is prepared, the greater the ratio of (003) to (110) peak intensity indicates that the positive electrode is The stronger the orientation of the composite, the more obvious the orientation of the C-axis of the composite cathode material perpendicular to the current collector; the smaller the ratio, the weaker the orientation of the C-axis of the cathode composite material perpendicular to the current collector, and its layered structure distribution is irregular, the more It is beneficial to slow down the thickness change of the pole piece due to the shrinkage and expansion of the unit cell volume during the charging and discharging process.
- the ratio of the 004 peak intensity to the 110 peak intensity can reach a minimum of 11.5 and a maximum of only 20, indicating that the positive electrode composite material prepared in the example
- the orientation of the electrode is poor, which is beneficial to slow down the expansion of the pole piece during charge and discharge; in terms of the compaction density after the cathode composite material is prepared for the pole piece, the higher the compaction density, the more conducive to the improvement of the battery energy density, and the compaction density The lower it is, it is not conducive to the performance of the energy density of the battery.
- the maximum compaction of the pole piece can reach 3.62g/cm 3
- the minimum can reach 3.45g/cm 3 .
- the pole piece has higher compaction, mainly the positive electrode composite material.
- Both the bulk material and the cladding material have high tap density.
- the capacity retention rate of 500 cycles of cycling at 45°C, the change rate of battery thickness after 28D storage at 60°C, the rate performance and the low-temperature discharge performance of the battery prepared from the positive electrode composite are mainly related to the particle size and coating material of NCM in the positive electrode composite.
- the particle size of the primary particles is related to the mass ratio between the bulk material and the cladding material in the composite material. The larger the particle size of NCM in the composite material, the larger the particle size of the primary particles of the coating material, the lower the degree of side reactions between the material and the electrolyte, the less gas produced by the material, and the amount of dissolved Mn in the coating material.
- the positive electrode composite material in the example has a maximum capacity retention rate of 94% and a minimum of 86% after being cycled at 45°C for 500 cycles. Has good high temperature performance.
- the 5C rate discharge ratio is up to 95%, and the lowest is 85%.
- the low temperature discharge ratio of -20°C is up to 85%, and the lowest can reach 78%.
- the composite cathode material has good low temperature and rate performance.
- Comparative Example 1 the proportion of LMFP in the composite cathode material is too high, and the two materials belong to different structures. During the charging and discharging process, the diffusion resistance of lithium ions is very large, and the high temperature cycle performance, rate and low temperature performance of the battery deteriorate. At the same time, the compaction of the pole pieces is also reduced.
- the positive electrode material is not coated, and the crystal orientation of the electrode sheet cannot be well suppressed.
- the electrode sheet expands and shrinks, which will cause uneven distribution of the electrolyte inside the battery and cause the battery. Lithium is deposited inside, and the cycle performance of the battery deteriorates.
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Abstract
Description
Claims (18)
- 一种用于电池的复合正极材料,其特征在于,包括:三元材料和相变材料,所述相变材料在所述三元材料的充放电区间存在相变平台,所述三元材料为单晶结构,所述相变材料为单晶结构或者团聚体结构,所述相变材料包覆在所述三元材料表面;所述三元材料与所述相变材料的质量分数比为80:20-99.8:0.2;所述三元材料的纳米硬度为0.001-5Gpa,所述相变材料的纳米硬度为0.01-10Gpa;所述三元材料的D50为3.0-6.0μm,所述相变材料的一次颗粒D50为10-50nm。
- 根据权利要求1所述的复合正极材料,其特征在于,所述三元材料的纳米硬度为0.2-1.4GPa,所述相变材料的纳米硬度为1.5-3.5GPa。
- 根据权利要求1所述的复合正极材料,其特征在于,所述三元材料的振实密度为2.0-2.8g/cm 3,所述相变材料的振实密度为0.8-1.5g/cm 3。
- 根据权利要求1所述的复合正极材料,其特征在于,所述三元材料的D50在3.5-5.0μm,所述相变材料的一次颗粒粒径D50在20-40nm。
- 根据权利要求1-4中的任一项所述的复合正极材料,其特征在于,所述三元材料的化学式为LiNi xCo yM z,其中x+y+z=1,M包括Mn、Al、Zr、Ti、Y、Sr或W。
- 根据权利要求1-5中任一项所述的复合正极材料,其特征在于,所述三元材料包括镍钴锰三元材料或镍钴铝三元材料。
- 根据权利要求1-4中的任一项所述的复合正极材料,其特征在于,所述相变材料为橄榄石结构,所述相变材料的化学式为LiA vB wPO 4,其中v+w=1,A包括Fe、Co、Mn、Ni、Cr或V,B包括Fe、Co、Mn、Ni、Cr或V。
- 根据权利要求7所述的复合正极材料,其特征在于,所述相变材料包括磷酸锰铁锂、磷酸锰钒锂或磷酸铬铁锂。
- 一种用于制作权利要求1-8中的任一项所述的复合正极材料的方法,其特征在于,包括:将一定质量比的三元材料、相变材料与NMP溶剂装入机械融合机进行融合形成复合材料;将融合后的所述复合材料在一定温度下进行烘烤,以得到所述复合正极材料,其中,所述三元材料为单晶材料,所述三元材料的粒径D50为3.0-6.0μm,所述相变材料为单晶材料或者二次球材料,所述相变材料的一次颗粒的粒径D50为10-50nm,所述三元材料与所述相变材料的质量分数比为80:20-99.8:0.2,所述三元材料的纳米硬度为0.001-5Gpa,所述相变材料的纳米硬度为0.01-10GPa。
- 根据权利要求9所述的方法,其特征在于,所述机械融合机的转速为4000-7000r/min,融合的时间为10-30min。
- 根据权利要求10所述的方法,其特征在于,所述机械融合机的转速为4500-6500r/min,融合的时间为15-25min。
- 根据权利要求9所述的方法,其特征在于,所述复合材料的烘烤温度为80-120℃,烘烤时长为0.5-2.5h。
- 根据权利要求12所述的方法,其特征在于,所述复合材料的烘烤温度为95-105℃,烘烤时长为1-2h。
- 一种用于电池的正极极片,其特征在于,包括集流体和设置在所述集流体上的如权利要求1-8中的任一项所述的复合正极材料。
- 根据权利要求14所述的正极极片,其特征在于,所述正极极片压片后晶体取向003/110的强度比为10-100。
- 一种用于制作权利要求14-15中的任一项所述的正极极片的方法,其特征在于,包括:在一定量的NMP溶剂中加入PVDF中形成PVDF溶液,所述PVDF的高分子链上具有含F基团和/或羧基、酯基、氨基;在所述PVDF溶液中,加入一定量的导电剂材料,并经过搅拌形成浆料;一定时长后,在所述浆料中加入权利要求1-8中的任一项所述的复合正极材料,进行充分搅拌,得到最终浆料;将最终浆料涂覆在集流体上,然后通过高温烘烤去除所述浆料中的所述NMP溶剂,并经辊压、切片得到正极极片。
- 根据权利要求16所述的方法,其特征在于,在得到最终浆料之前,还包括:在所述浆料中加入一定量的碳酸锂。
- 一种电池,其特征在于,包括:权利要求14或15所述的正极极片,负极极片,以及设置在所述正极极片和负极极片之间的隔膜。
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