WO2023011623A1 - 电极、电极的制备方法和电池 - Google Patents

电极、电极的制备方法和电池 Download PDF

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WO2023011623A1
WO2023011623A1 PCT/CN2022/110517 CN2022110517W WO2023011623A1 WO 2023011623 A1 WO2023011623 A1 WO 2023011623A1 CN 2022110517 W CN2022110517 W CN 2022110517W WO 2023011623 A1 WO2023011623 A1 WO 2023011623A1
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layer
electrode
particles
pole piece
layers
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PCT/CN2022/110517
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English (en)
French (fr)
Chinese (zh)
Inventor
袁晓涛
许占
陈培兴
吴煊伟
何科峰
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BYD Co Ltd
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BYD Co Ltd
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Priority to KR1020247000230A priority Critical patent/KR20240016425A/ko
Priority to JP2023578974A priority patent/JP2024527703A/ja
Priority to EP22852334.6A priority patent/EP4345932A4/en
Priority to AU2022324509A priority patent/AU2022324509B2/en
Publication of WO2023011623A1 publication Critical patent/WO2023011623A1/zh
Priority to US18/399,468 priority patent/US20240290970A1/en
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    • 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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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • H01M2004/027—Negative electrodes
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    • H01M2004/028—Positive electrodes
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    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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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 application relates to the technical field of battery components, and more specifically, to an electrode, a method for preparing the electrode, and a battery.
  • Lithium-ion power battery is a new type of high-energy battery that can be charged, mainly relying on lithium ions to move between the positive and negative electrodes to work. It has the advantages of high energy, high battery voltage, wide operating temperature range, and long storage life, and has been widely used in military and civilian small electrical appliances.
  • the volumetric energy density of a lithium-ion power battery is critical to its use in a complete vehicle.
  • the compaction density of the electrodes is usually increased to increase the volumetric energy density of the battery.
  • the ultimate compaction density of the electrode is usually affected by the true density of the material itself.
  • the porosity of the electrode will become extremely low, especially on the surface of the electrode. The pores are easily blocked, making it difficult for lithium ions to Diffusion leads to a significant decrease in the kinetic performance of the electrode.
  • One purpose of the present application is to provide an electrode, a preparation method of the electrode and a new technical solution of the battery.
  • an electrode including: n layers of pole piece layers stacked in sequence; wherein, the pole piece layer on the side close to the separator of the battery is the first layer, and one side close to the current collector of the battery
  • the pole piece layer on the side is the nth layer, and n is a natural number greater than or equal to 2;
  • the electrode material of the pole piece layer in the first layer includes first particles, and the pole pieces in each layer of the second to n layers
  • the electrode material of the layer includes at least a first particle and a second particle respectively, and the average particle diameter of the first particle is larger than the average particle diameter of the second particle; the porosity of each layer of the pole plate is along the The direction of layer to layer 1 gradually increases.
  • a method for preparing the electrode described in the first aspect comprising the following steps: fully mixing the electrode material with a conductive agent and a binder to form a mixture; heating the mixture to make the The binder is in a molten state; the binder in the molten state is solidified, and the solidified binder wraps the electrode material to obtain a powdery substance; the powdery substance is processed to form the pole piece layer; according to In the above manner, by adjusting the number of the first particles and the second particles of each layer of the pole piece layer, multiple layers of the pole piece layer with different porosities are prepared; according to the size of the porosity, the multiple layers of the pole piece layer The pole piece layers are sequentially stacked and fused to obtain the electrode.
  • a battery including the electrode described in the first aspect.
  • the electrode sheet layer on the side of the diaphragm is prepared by the first particles, and the remaining electrode sheet layers are prepared by the first particles and the second particles with different particle sizes, thereby increasing the compaction density of the electrode.
  • the multi-layer arrangement of the pole piece layer, and the porosity of each pole piece layer is set to gradually increase along the direction from the current collector side to the separator side layer, which improves the diffusion efficiency of lithium ions and improves the efficiency of lithium ion diffusion. the kinetic performance of the electrode.
  • Fig. 1 is a schematic diagram of an electrode and its preparation process in the present application.
  • Fig. 2 is a schematic diagram of a battery in the present application.
  • Fig. 3 is a flow chart of the preparation method of the electrode in the present application.
  • the volumetric energy density of the battery is usually increased by increasing the compaction density of the electrode, but the high compaction of the electrode will reduce the porosity of the electrode, especially the pores on the electrode surface are easily blocked.
  • the amount of pores in the electrode will directly affect the charging and discharging performance of the battery. If the porosity is low or blocked, it will affect the movement of lithium ions, resulting in a significant decrease in the kinetic performance of the electrode. Therefore, the electrode structure not only needs to have high voltage, but also needs to have a reasonable pore structure.
  • the porosity refers to the percentage of the pore volume in the material to the total volume of the material in the natural state.
  • the present application provides an electrode, including n layers of pole piece layers stacked in sequence; wherein, the pole piece layer on the side close to the separator of the battery is the first Layer 13, the pole piece layer near the current collector side of the battery is the nth layer 14, n is a natural number greater than or equal to 2; the electrode material of the pole piece layer of the first layer 13 includes first particles 11, The electrode material of each pole sheet layer of the second to n layers includes at least first particles 11 and second particles 12 respectively, and the average particle diameter of the first particles 11 is greater than the average particle diameter of the second particles 12 ; The porosity of each pole piece layer gradually increases along the direction from the nth layer 14 to the first layer 13 .
  • the electrode is a structure in which multiple layers (n layers) of pole pieces are stacked (n is a natural number greater than or equal to 2, that is, the electrode can include 2 layers, 3 layers, or even more layers.
  • n is a natural number greater than or equal to 2
  • this structure is beneficial to distinguish the characteristics such as the electrode material of each pole piece layer.
  • the electrode sheet layer After the multi-layer electrode sheet layer is stacked and set, determine the electrode sheet layer of the first layer 13 and the electrode sheet layer of the nth layer 14 that are respectively located on both sides of the electrode (when the electrode is applied to the battery, the two sides of the electrode are usually set
  • the current collector and the separator, the pole piece layer close to the current collector is the nth layer 14, and the pole piece layer close to the diaphragm is the electrode material of the first layer 13).
  • the electrode material includes first particles 11 and second particles 12 , wherein the average particle diameter of the first particles 11 is larger than the average particle diameter of the second particles 12 .
  • the electrode material of the first layer 13 pole sheet layer can only include the first particle 11, and the electrode material of the remaining pole sheet layers (2nd to n layers) can include the first particle 11 (large particle) and the second particle 12 (small particle) ).
  • the combination of large particles and small particles enables small particles to fill the gaps between large particles to achieve higher compaction density.
  • the remaining pole piece layers refer to other pole piece layers except the first layer 13, that is, if the electrode has two pole piece layers in total, and the remaining pole piece layers are the second pole piece layer, then the second pole piece layer
  • the electrode material of the sheet includes at least the first particle 11 and the second particle 12; if the electrode has 3 pole layers, and the remaining pole layers are the second and third layers, then the second and third layers
  • the pole piece layers of the three layers respectively include at least the first particles 11 and the second particles 12 , and so on.
  • each pole piece layer can be controlled gradually along the direction from the nth layer 14 to the first layer 13 by adjusting the number of large and small particles in the remaining pole piece layers (the second to n layers). increase, that is, the pole piece layer of the nth layer 14 has the lowest porosity, while the diaphragm layer side has larger pores and higher porosity, so as to facilitate the diffusion of lithium ions, so that the electrode has lower impedance and higher porosity. High discharge retention rate.
  • the more layers there are in the pole sheet the more uniform the gradient distribution of the pores (that is, the variation law in which the porosity gradually increases along the direction from the nth layer 14 to the first layer 13) is more uniform, which is more conducive to the diffusion of lithium ions .
  • the particle diameters of the first particles 11 selected in each layer of the pole sheet can be different, and correspondingly, the particle diameters of the second particles 12 selected in the second to n layers can also be different, so as to facilitate the construction of each layer of the pole sheet different porosity.
  • the diffusion of lithium ions is limited by the layer with lower porosity.
  • the pole of the first layer 13 of the electrode can be determined first.
  • the electrodes in this example have a high compaction density, which increases the volumetric energy density of the lithium-ion battery.
  • the gradient change law of porosity between the pole piece layer of the first layer 13 and the pole piece layer of the nth layer 14 makes the electrode in this solution have higher dynamic performance at the same time.
  • the number ratio of the first particles 11 included in the pole piece layer of the xth layer in the electrode material of this layer is a, then:
  • n is a natural number greater than or equal to 2
  • x is a natural number less than or equal to n
  • m is the number of particles.
  • the porosity of each pole piece layer can be realized by adjusting the quantity of the first particles 11 and the second particles 12 in each layer.
  • the gradient change of the porosity of each pole sheet layer is realized by adjusting the number of large and small particles, which is easy to realize in actual production, and the adjustment result is relatively accurate.
  • the first particles 11 in the pole piece of the first layer 13 account for 100%
  • the first particles 11 in the pole piece of the second layer account for 50%.
  • the proportion of first particles 11 in the pole piece layer of the first layer is 100%
  • the proportion of first particles 11 in the pole piece layer of the second layer is 83.3%.
  • the first particles 11 in the pole piece layer of the third layer accounted for 66.7%, and the first particles 11 in the pole piece layer of the fourth layer accounted for 50%.
  • the number of first particles 11 is set, and the number of first particles 11 in the pole layer of the nth layer 14 can always be kept at least 50%, so as to ensure that the porosity of each pole layer does not vary. would be too low.
  • the average particle diameter of the first particles 11 ranges from 0.90 to 1.60 ⁇ m
  • the average particle diameter of the second particles 12 ranges from 0.25 to 0.70 ⁇ m.
  • the average particle diameter of the first particles 11 ranges from 0.90 to 1.60 ⁇ m
  • the average particle diameter of the second particles 12 ranges from 0.25 to 0.70 ⁇ m. If the average particle size of the first particles 11 or the second particles 12 is too large, the specific surface area of the particles will be smaller, the solid phase diffusion path will increase, the electrochemical reaction kinetics of the material will be slower, and the kinetic performance of the battery will be affected. And if the average particle size of the first particle 11 or the second particle 12 is too small, the specific surface area of the particle will be larger, and the electrochemically active area will be larger accordingly, so that the side reactions on the surface of the particle material will increase. , the cycle performance of the battery is impaired.
  • the electrochemically active area refers to the sites on the particle surface that can participate in electrochemical reactions.
  • the average particle diameter of the first particles 11 is in the range of 1.0-1.2 ⁇ m
  • the average particle diameter of the second particles 12 is in the range of 0.35-0.55 ⁇ m.
  • the radius of the first particle 11 is R
  • the radius of the second particle 12 is less than or equal to 0.414R.
  • the electrode materials used can be approximately regarded as spherical particles.
  • the electrode materials used can be approximately regarded as spherical particles.
  • the compaction of the material can be further improved. That is, in the case of close packing of the first particles 11 , if the radius of the first particles 11 is R, the maximum radius that the pores of the first particles 11 can hold is 0.414R. Therefore, when the radius r ⁇ 0.414R of the second particles 12 , they can be smoothly filled into the pores between the first particles 11 .
  • the material combined in this way has ultra-high compaction, and the material combined by this ultra-high compaction can be used as the pole piece layer of the nth layer 14, and then from the pole piece layer of the nth layer 14 to the pole piece layer of the first layer 13
  • the filling amount of the second particles 12 can be gradually reduced to gradually increase the porosity of each layer and construct a gradient pore structure that facilitates the diffusion of lithium ions.
  • Such an electrode structure can take into account both high compaction and high particle diffusion efficiency.
  • each pole piece layer of the second to n layers further includes third particles, and the maximum radius of the third particles is less than or equal to 0.225R.
  • the other pole piece layers can also be prepared from three kinds of granular materials with different sizes.
  • the pole piece layer of the nth layer 14 can be prepared by using the first particles 11 , the second particles 12 and the third particles.
  • the maximum radius of the third particle is 0.225R. Higher compaction of the pole sheet layer constructed using three different sized granular materials.
  • the filling quantity of the second particles 12 and/or the third particles can be gradually reduced from the pole piece of the nth layer 14 to the pole piece of the first layer 13 , to gradually increase the porosity of each layer to construct a gradient pore structure that facilitates the diffusion of lithium ions.
  • the use of three kinds of granular materials can not only increase the compaction density of the electrode, but also facilitate the adjustment of the change gradient of the porosity, which is beneficial to realize the uniform change of the pore structure of each layer.
  • the particle size of the first particle 11 and the particle size of the second particle 12 used in the pole piece layer of the xth layer meet the following conditions:
  • x is a natural number greater than 1 and less than or equal to 2, and a is the number ratio of the first particles 11 in the xth layer in the electrode material of this layer; d11 represents the first particle of the pole piece layer of the first layer 13 The particle size of the particle 11, dx1 represents the particle size of the first particle 11 of the x-th layer of the polar layer; dx2 represents the particle size of the second particle 12 of the x-th layer.
  • the tortuosity of each pole layer can be adjusted by adjusting the particle size of the first particles 11 and the second particles 12 of each layer. ⁇ is similar. That is, the particle diameter of the first particles 11 in the pole piece layer of the first layer 13 may be different from that of the first particles 11 in the pole piece layers of the remaining second to n layers.
  • the tortuosity ⁇ is used to describe the parameters of the electrode pore structure, the greater the tortuosity, the more tortuous the internal pores, and the longer the path for ions to diffuse from the surface to the current collector.
  • the number of layers of the pole piece layer ranges from 2 to 10 layers, and the number of second particles 12 included in the electrode material of each pole piece layer except the first layer 13 is along the direction from the current collector to the current collector. It gradually decreases from the side to the side close to the diaphragm.
  • the number of pole piece layers can be selected from 2 to 10 layers to construct a uniform pore structure. If the number of pole sheet layers is too large, the change in porosity between adjacent two layers is very small, and the gradient change of too small porosity is not particularly effective in improving the diffusion of lithium ions, but it has an impact on production efficiency. But big. Therefore, the appropriate selection of layers can take into account the gradient change of porosity and production efficiency. In addition, by adjusting the proportion of the second particles 12 in each layer, the gradient adjustment of porosity can be realized.
  • the electrode material includes a positive electrode material, and the positive electrode material is at least one of lithium iron phosphate, lithium nickel cobalt manganese oxide and lithium manganate.
  • the electrode provided in this embodiment can be made of positive electrode material and used as the positive electrode of the battery, or can be made of negative electrode material and used as the negative electrode of the battery.
  • the positive electrode material can be at least one of lithium iron phosphate, lithium nickel cobalt manganese oxide and lithium manganate;
  • the negative electrode material is at least one of artificial graphite, natural graphite, lithium titanate, soft carbon and hard carbon.
  • the double-layer electrode scheme is adopted, and the electrode material is lithium iron phosphate material.
  • the three-layer electrode scheme is adopted, and the electrode material is lithium iron phosphate material.
  • the average particle diameter of the first particle 11 is 1.30 ⁇ m
  • the average particle diameter of the second particle 12 is 0.53 ⁇ m
  • the mass ratio is 97:3
  • the three-layer electrode scheme is adopted, and the electrode material is lithium iron phosphate material.
  • the average particle size of the first particle 11 is 1.12 ⁇ m
  • the average particle size of the second particle 12 is 0.466 ⁇ m
  • the mass ratio is 97:3
  • the double-layer electrode scheme is adopted, and the electrode material is lithium iron phosphate material.
  • the single-layer electrode scheme is adopted, and the electrode material is lithium iron phosphate.
  • Example Compaction density under the same rolling pressure (g/cm 3 ) Example 1 2.702.65
  • Table 1 shows the compaction density corresponding to an electrode with a width of 5 cm under a rolling pressure of 1 MPa. It can be seen that despite the addition of small particles (second particles 12), the design of multi-layer coating can make the compaction of the pole piece still maintained at a relatively high level.
  • Example 0.33C discharge mixed gram capacity (mAh/g) Example 1 137.5
  • Example 3 138.2 Comparative example 1 135.8 Comparative example 2 137.2 Comparative example 3 136.8
  • Table 2 shows the electrodes obtained by multi-layer coating according to the gradient porosity design, and the electrodes obtained by the multi-layer coating gradient porosity design have higher capacity performance under the same design parameters.
  • 50% SOC Table 3 shows that under the condition of 50% SOC DC internal resistance, the electrode in this application has lower impedance, which is beneficial to the diffusion of lithium ions.
  • Example 0.2C/2C discharge ratio Example 1 0.940
  • Example 2 0.959
  • Example 3 0.960 Comparative example 1 0.875 Comparative example 2 0.898 Comparative example 3 0.918
  • Table 4 shows that under the condition of 0.2/2C discharge capacity ratio at room temperature, the electrode of the present application has a higher discharge retention rate, which is beneficial to the diffusion of lithium ions.
  • the pole piece layer with multiple layers of different porosity is prepared;
  • the electrodes are obtained by sequentially stacking and merging multiple pole pieces.
  • the positive electrode material can be lithium iron phosphate, lithium nickel cobalt manganese oxide, lithium manganate, etc.
  • the conductive agent includes carbon nanotubes, graphene, carbon black, carbon fiber, etc.
  • the powdered material is processed to form a basic pole piece of a specific size and thickness, which is the pole piece layer that is finally used to process electrodes.
  • the prepared multi-layer pole pieces are stacked and fused, and finally an electrode with high compaction and uniform porosity change is obtained.
  • the electrode material when preparing the first layer 13 pole sheet layer, the electrode material only needs to be added with the first particle 11, and the remaining layers can be added with the first particle 11, the second particle 12 or even according to the actual needs according to the technical solution of the first aspect In the third particle and so on.
  • the quantity ratio of the first particle 11 and the second particle 12 of each pole layer can be determined by formula (1), and the particle diameter of the first particle 11 and the second particle 12 of each pole layer can be determined by formula (2) .
  • the electrode prepared by the preparation method of the present application has an ultra-high compaction density, so that the volumetric energy density of the battery is improved.
  • the porosity of the electrode layer from the first layer 13 to the nth layer 14 has a certain gradient change law, which can ensure the dynamic performance of the electrode at the same time.
  • the whole preparation process is simple and the preparation efficiency is high.
  • solidifying the binder in a molten state includes: solidifying the binder into a fiber shape through an electrospinning process.
  • Electrospinning is a special form of electrostatic atomization of polymer fluids.
  • the substances split by atomization are not tiny droplets, but tiny jets of polymers, which can run for a long distance and finally solidify into fibers.
  • polymer filaments with nanoscale diameters can be produced, resulting in a stronger and more uniform bond between the binder and the particles of the electrode material.
  • the process of sequentially stacking and fusing multiple pole piece layers includes: a hot pressing process.
  • the hot-pressing process can realize high-pressure compaction of the granular material, on the other hand, it can make the fusion of each layer more complete, and make the integrity of the electrode stronger.
  • a battery including the electrode described in the first aspect.
  • the battery includes: a first current collector, a first electrode 1, a separator, a second electrode 2, and a second current collector arranged in sequence, and the first electrode 1 and the second electrode 2 are respectively connected to the Electrolyte is arranged between the separators.
  • the battery provided in this embodiment includes a first current collector 4, a first electrode 1, a separator 3, a second electrode 2, and a second current collector 5 arranged in sequence, and the first electrode 1 and the second electrode 2 An electrolyte solution 6 is provided between the separators 4 respectively.
  • the first electrode 1 is a negative electrode
  • the second electrode 2 is a positive electrode, both of which adopt the electrode structure described in the first aspect.
  • the pole piece layers of the first layer 13 of the first electrode 1 and the second electrode 2 are arranged close to the diaphragm 3 , while the pole piece layers of the nth layer 14 are close to the first current collector 4 and the second current collector 5 respectively.
  • the first current collector 4 can be made of copper foil
  • the second current collector 5 can be made of aluminum foil.
  • the battery in this example has higher volumetric energy density and kinetic performance.

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