CN114725369A - High-energy-density positive electrode material, positive electrode plate and lithium ion battery - Google Patents
High-energy-density positive electrode material, positive electrode plate and lithium ion battery Download PDFInfo
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- CN114725369A CN114725369A CN202210123971.XA CN202210123971A CN114725369A CN 114725369 A CN114725369 A CN 114725369A CN 202210123971 A CN202210123971 A CN 202210123971A CN 114725369 A CN114725369 A CN 114725369A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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Abstract
The invention provides a high-energy-density positive pole material, a positive pole piece and a lithium ion battery, wherein the positive pole material contains a positive active substance and an additive, the positive pole piece comprises a metal current collector and a positive pole material, the additive is directly coated on the metal current collector together with the positive active substance, or the micrometer-level thickness additive is sprayed on the pole piece with the positive active substance, the lithium ion battery comprises a battery shell, a pole core and electrolyte, the pole core and the electrolyte are sealed in the battery shell, the pole core comprises a positive pole, a negative pole and a diaphragm positioned between the positive pole and the negative pole, and the positive pole comprises the positive current collector and the high-energy-density positive pole material positioned on the positive current collector. The invention adopts specific additives in the anode material, which has extremely high theoretical specific capacity and actual specific capacity; the consumption of an SEI film of a negative electrode can be supplemented by active lithium with irreversible capacity, the energy density of the power battery can be improved, and the service life of the power battery can be prolonged; the potential safety hazard of the common lithium supplementing technology is avoided.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-energy-density positive electrode material, a positive electrode plate and a lithium ion battery.
Background
In recent years, the new energy market is continuously developed and matured, and with the improvement of the endurance requirement of the whole vehicle, the demand of the lithium ion battery with high energy density is remarkably increased. Meanwhile, the usage scenarios of new energy vehicles are becoming more abundant, for example, after retired from a vehicle, lithium ion batteries are used for cascade utilization of logistics vehicles, buildings and base stations, and the service life of the lithium ion batteries needs to be further prolonged.
However, since the negative active material of the lithium ion battery is mainly a graphite negative electrode, the intercalation potential of the graphite negative electrode is lower than the reduction potential of organic electrolytes such as PC, EC, DEC. Therefore, the electrolyte is reduced during the first charging process to form a Solid Electrolyte Interface (SEI) on the surface of the negative electrode, and the SEI not only participates in electrons, but also participates in lithium ions. For example, LiF, Li are formed2CO3Namely, lithium-containing organic materials such as alkyl lithium carbonate. Because the graphite cathode does not contain lithium in the lithium ion battery, the anode is used as the only lithium supply source in the SEI forming process, 7% -15% of active lithium loss can be caused, and the energy density and the service life of the power battery are further influenced.
In order to improve the energy density and the service life of the power battery, extensive lithium supplement technical research provides various solutions. For example, lithium is replenished from a slurry, that is, metallic lithium, an organic material containing lithium, a modifying material, or the like, a negative electrode material, and a nonaqueous liquid are mixed to form a slurry, and the slurry is applied to a current collector, followed by drying, rolling, injection, or the like. Although the method can improve the energy density of the lithium ion battery, the metallic lithium has high reaction activity and is easy to react with oxygen and moisture in the air. Therefore, the control requirement for moisture in the preparation process is also extremely strict, thereby increasing the process difficulty. Meanwhile, the lithium ion battery has extremely high requirements on the purity of various materials, and once impurities are introduced into the lithium-containing material, the lithium-containing material can have adverse effects on the performance of the battery. Or by surface treatment, but is limited by too high activity and difficulty in using the operation time of the pre-process of lithium ion battery manufacturing. Meanwhile, the lithium powder is easy to float in the air, and great potential safety hazard exists. Or materials such as lithium-rich lithium salt, lithium oxide, lithium-containing organic matter and the like are adopted to perform material level lithium supplement on the positive electrode, but the problem of activity of the lithium supplement material and the problem of utilization rate of lithium ions bring great difficulty to practical application.
The prior art discloses a pole piece lithium supplementing method and system, which increase the base material for a metal lithium piece or a lithium belt, on one hand, the strength of the lithium belt is enhanced, and on the other hand, the separation is formed between the lithium belt and a composite device, so that the lithium belt can not be in direct contact with the composite device in the conveying process, and the lithium belt is prevented from being torn off or pinched off in the production process. However, the method has extremely high requirements on the environment in the manufacturing process so as to avoid the reaction of the lithium metal with air and water, so the practical application difficulty is higher.
The prior art also discloses a negative electrode lithium supplement slurry, a negative electrode and a lithium secondary battery, wherein the lithium supplement slurry is prepared by adopting metal lithium powder and a prepolymer, the lithium supplement slurry is coated on a prepared negative electrode plate, the prepolymer in the lithium supplement slurry is subjected to polymerization reaction under the conditions of illumination or heating and the like to form a macromolecular polymer, and then the lithium supplement negative electrode plate is obtained by cold pressing. However, the method increases the manufacturing complexity of the lithium ion battery, and the uniformity of the lithium supplement slurry of the metal lithium powder and the prepolymer and the dispersion degree in the mass production process are difficult to maintain uniform, so that the uniformity of the manufactured battery cell is reduced due to the easy occurrence of sedimentation.
The prior art also discloses a method for supplementing lithium to the lithium ion battery positive plate, and the method realizes 'wet lithium supplementation' by spraying or dripping uniform organic lithium solution on the surface of the positive plate, thereby effectively avoiding the floating of metal lithium powder in the air when lithium is supplemented by a dry method, ensuring the production safety, and the whole process is simple and low in cost. However, the lithium supplement of the method needs to be carried out in an inert atmosphere to ensure the stability of the high-activity organic lithium solution, so the practical application difficulty is higher.
Disclosure of Invention
The invention aims to provide a high-energy-density positive electrode material, a positive electrode plate and a lithium ion battery aiming at the defects of the prior art, and mainly solves the problems of low efficiency, complex operation process and certain potential safety hazard of the existing lithium supplement mode of the lithium ion battery.
The purpose of the invention is realized by the following technical scheme:
the high-energy-density cathode material contains a cathode active substance and an additive, wherein the additive is Li2NixMyO2Core-shell materials of @ LFP-X, i.e. in Li2NixMyO2The exterior of the material is coated with a layer of LFP-X material through physical or chemical coating; wherein x is more than 0 and less than or equal to 1, y is 1-x, and M is a metal element such as Cu, Al, Fe, Mn, Co, Ti, Sb, Mg and the like or a nonmetal element such as B, F and the like. Further, the LFP-X shell material is a pure phase LiFePO4 material or a pure phase LiFePO4 metal-doped LFP-X material, wherein X may be Mg, Mn, Al, Ti, V, Nb, Sb, or other metals.
Further, the Li2NixMyO2@ LFP-X material, made by chemical or physical means, Li2NixMyO2The particle size of the @ LFP-X material is 1-10um, wherein Li2NixMyO2The grain diameter of the core material is 0.5-9.5um, LFP-X shell materialThe particle size of (A) is 0.5-5 um.
Furthermore, the chemical method is a solid phase method or a liquid phase method, and the solid phase method is selected from a high-temperature solid phase reaction method, a carbothermic method, a microwave synthetic beam and a pulse laser deposition method, a sol-gel method, a hydrothermal synthesis method, a precipitation method and a solvothermal synthesis method; the physical method adopts high-energy ball milling and physical vapor deposition.
Further, the Li2NixMyO2The lithium source selected in the preparation process of the @ LFP-X material is Li2CO3、LiOH、Li2O、CH3COOLi、LiNO3And Li2C2O4One or more of (A), the iron source is Fe2O3、FeOOH、Fe(OH)3、Fe(NO3)3、Fe2(SO4)3One or more of NiO and NiO as nickel source2、NiOOH、Ni(OH)2、NiNO3、Ni2SO4In the case where M is a metal element such as Cu, Al, Fe, Mn, Co, Ti, Sb or Mg, MOx, MO (OH) x or M (NO) is used as the metal source3)x、M(SO4) x, wherein x depends on the valence state of the metal element.
A positive pole piece comprises a metal current collector and a high-energy-density positive pole material, wherein an additive is directly coated on the metal current collector together with a positive active substance, or the micrometer-level thickness of the additive is sprayed on the pole piece with the positive active substance.
Furthermore, the mass percentage of the additive to the positive active material is a, and a is more than 0% and less than or equal to 50%.
Furthermore, the mass percentage of the additive to the positive electrode active material is 5% -15%.
Furthermore, the additive is prepared into slurry, and then is coated on the surface of the positive active material pole piece by a spraying method, a screen printing method and a blade coating method, wherein the thickness of the positive active material pole piece is 1-10 um.
The utility model provides a lithium ion battery, lithium ion battery includes battery case, utmost point core and electrolyte are sealed in the battery case, the utmost point core includes anodal, negative pole and is located the diaphragm between anodal and the negative pole, anodal including the anodal mass flow body and the high energy density cathode material who is located the anodal mass flow body.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a high-energy-density positive electrode material, a pole piece and a lithium ion battery2NixMyO2Core-shell materials of @ LFP-X, where Li2NixMyO2Has extremely high theoretical specific capacity and actual specific capacity which can reach 300-600 mAh/g;
2. meanwhile, after charging and lithium removal, due to the structural damage of the lithium-rich material, part of lithium ions can not be inserted back during discharging, so that the lithium-rich lithium ion battery has higher charging capacity and lower discharging capacity, and the consumption of an SEI (solid electrolyte interphase) film of the negative electrode is supplemented by active lithium with irreversible capacity;
3. the residual reversible capacity of the additive material can be used as a positive active substance in the using process of the battery, so that the energy density of the power battery is improved, and the service life of the power battery is prolonged;
4. in addition, since in Li2NixMyO2The LFP-X material is physically or chemically coated outside the material, so that the additive can be ensured to be the same as the processing method of a common positive active substance in the production process of a lithium ion battery, and can be directly coated on a positive metal current collector together with the positive active substance or a positive pole piece with high energy density is prepared by coating the additive material with micron-level thickness on the pole piece with the positive active substance, no additional manufacturing procedure or environmental control is needed, the method is easier to realize in actual production, and the problem of potential safety hazard of a common lithium supplement technology is avoided.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is Li2NixMyO2A schematic of a core-shell material of @ LFP-X;
FIG. 2 is a schematic view of a high energy density positive electrode sheet;
FIG. 3 is a first charge and discharge curve of a lithium ion battery.
Detailed Description
The invention is further illustrated by the following examples:
the present invention will be described in further detail with reference to the accompanying drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention. It should be further noted that, for the convenience of description, only some of the structures related to the present invention are shown in the drawings, not all of the structures.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures. Meanwhile, in the description of the present invention, the terms "first", "second", and the like are used only for distinguishing the description, and are not to be construed as indicating or implying relative importance.
As shown in FIG. 1, the invention provides a high-energy-density cathode material, which contains a cathode active material and an additive, wherein the additive is Li2NixMyO2Core-shell materials of @ LFP-X, i.e. in Li2NixMyO2The exterior of the material is coated with a layer of LFP-X material through physical or chemical coating. Wherein x is more than 0 and less than or equal to 1, y is 1-x, and M is a metal element such as Cu, Al, Fe, Mn, Co, Ti, Sb, Mg and the like or a non-metal element such as B, F and the like, so that the specific capacity of the alloy can reach 300-600mAh/g, even higher.
Meanwhile, after the charging and the lithium removal, because the structure of the lithium-rich material is damaged, part of lithium ions can not be inserted back during the discharging, so that the lithium-rich lithium ion battery has higher charging capacity and lower discharging capacity, and the consumption of the SEI film of the negative electrode is supplemented by active lithium with the irreversible capacity.
The residual reversible capacity of the additive can be used as a positive active substance in the use process of the battery, so that the energy density of the power battery is improved, and the service life of the power battery is prolonged. The additive is in Li2NixMyO2The LFP-X material is physically or chemically coated outside the material, so that the stability of the additive in the air is ensured, and the same processing method as that of a common positive active substance can be realized in the storage or manufacturing process.
The LFP-X shell material can be a pure-phase LiFePO4 material or a pure-phase LiFePO4 metal-doped LFP-X material, wherein X can be Mg, Mn, Al, Ti, V, Nb, Sb and other metals, so that the conductivity of the interior of a pure-phase LiFePO4 crystal is improved.
The Li2NixMyO2The @ LFP-X material can be synthesized by chemical methods, such as a solid phase method, namely a high-temperature solid phase reaction method, a carbothermic method, a microwave synthesis method and a pulse laser deposition method; or a liquid phase method such as a sol-gel method, a hydrothermal synthesis method, a precipitation method, and a solvothermal synthesis method. Physical methods such as high energy ball milling, physical vapor deposition, and the like may also be used. Li2NixMyO2The particle size of the material is 1-10um @ LFP-X, wherein Li2NixMyO2The grain diameter of the core material is 0.5-9.5um, and the grain diameter of the LFP-X shell material is 0.5-5 um.
The Li2NixMyO2The lithium source selected in the preparation process of the @ LFP-X material can be Li2CO3、LiOH、Li2O、CH3COOLi、LiNO3And Li2C2O4One or more of (a).
The L Li2NixMyO2The iron source selected in the preparation process of the @ LFP-X material can be Fe2O3、FeOOH、Fe(OH)3、Fe(NO3)3、Fe2(SO4)3One or more of (a).
The Li2NixMyO2The nickel source selected in the preparation process of the @ LFP-X material can be NiO or NiO2、NiOOH、Ni(OH)2、NiNO3、Ni2SO4One or more of (a).
The Li2NixMyO2The metal source used in the preparation of the @ LFP-X material, i.e. M is Cu, Al, Fe, Mn, Co, Ti, Sb, Mg, etc., MOx, MO (OH) X, M (NO) can be used3)x、M(SO4) x, wherein x depends on the valence state of the metal element.
The additive and the positive electrode active material are subjected to slurry preparation and coated on the positive electrode metal current collector, wherein the mass percentage of the additive to the positive electrode active material is a, and a is more than 0% and less than or equal to 50%, preferably 5% -15%, the slurry preparation and coating process is the same as the known general technology in the industry, and no extra environmental control and process procedures are needed, as shown in fig. 2.
The additive material is prepared into slurry by adopting the known general technology in the industry, and the slurry is coated on the surface of the positive active material pole piece by a spraying method, a screen printing method and a blade coating method, wherein the thickness of the slurry is 1-10um, and the thickness is shown in figure 2.
The invention provides a high-energy-density positive pole piece, which comprises a metal current collector and a positive pole material, wherein an additive can be directly coated on the metal current collector together with a positive active substance, or the micrometer-level 1-10 um-thick additive material is coated on the pole piece with the positive active substance.
The additive has high stability, the particle size and the surface energy of the additive are similar to those of common positive electrode materials, the preparation of slurry and the coating of the slurry on a positive electrode metal current collector can be directly carried out together with a positive electrode active substance, additional manufacturing procedures or environmental control are not needed, the preparation is easier to realize in actual production, and the problem of potential safety hazard of a common lithium supplement technology is avoided.
The lithium ion battery positive electrode active material is characterized in that the additive can be independently prepared into lithium supplement slurry, a micrometer-level additive material is sprayed and transfer-coated on a positive electrode active material-containing pole piece, the thickness can be 1-10 micrometers, after the first charging and lithium removal, a protective layer with higher stability is formed on the surface of the positive electrode active material of the pole piece, the safety of the lithium ion battery under abuse conditions is improved, and meanwhile, the uniformity of additive distribution on the pole piece is guaranteed by the aid of the independent additive slurry.
The high-energy-density positive electrode material and the positive electrode plate can be used for preparing a lithium ion battery, the positive electrode material is lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickelate, lithium manganese rich base, ternary nickel cobalt manganese and ternary nickel cobalt aluminum, and the negative electrode material is graphite, metal lithium and alloy. Meanwhile, the lithium ion battery can be used for lithium ion batteries with different packaging types, including hard shell square type, soft package and cylindrical type.
The invention provides a lithium ion battery which comprises a battery shell, a pole core and electrolyte, wherein the pole core and the electrolyte are sealed in the battery shell, the pole core comprises a positive pole, a negative pole and a diaphragm positioned between the positive pole and the negative pole, the positive pole comprises a positive pole current collector and a positive pole material positioned on the positive pole current collector, and the positive pole material is the positive pole material provided by the invention.
The lithium ion battery adopts the anode material provided by the invention, namely the anode material contains an anode active substance and an additive material, and the mass percent of the additive and the anode active material is a by matching calculation with the design of a cathode, wherein a is more than 0% and less than or equal to 50%, and preferably 5% -15%. The additive has no kind requirement on the anode material, such as LFP, NCM, LMO, LTO and the like which are commonly used in the industry, and has wide application range.
The additive has no kind requirement on the negative electrode material, such as Gr, LTO, Gr-nano Si and Gr-SiO which are commonly used in the industryxAnd the like, and the application range is wide.
The additive has no variety requirements on diaphragm materials, such as PP, PE, ceramic coating, PVDF coating modified diaphragm and the like which are commonly used in the industry, and has wide application range.
The additive has no kind requirements on electrolyte materials, such as LiPF6, LiBOB, LiFSI electrolyte and the like which are commonly used in the industry, EC, DEC, DMC organic solution and the like, and has wide application range.
Compared with the prior art, the high-energy-density positive electrode material, the pole piece and the lithium ion battery have at least the following improvements:
1. the additive content is obviously improved, the lithium supplementing efficiency is greatly improved, and simultaneously, the energy density and the service life of the lithium ion battery are greatly improved.
2. The stability of the lithium supplement additive material is obviously improved, and compared with the raw material containing a metal lithium belt and lithium powder, the problem of potential safety hazard is avoided.
3. Compared with other lithium supplementing methods, the processing process has obviously reduced complexity. The method is easy to realize in actual production without providing additional manufacturing procedures or environmental control.
Example 1
Mixing Li in a molar ratio of 1-1.5:12O, NiO is used as raw material, sintering is carried out under the protection of argon gas, the heating speed is 5 ℃/min, the sintering temperature is 600 ℃ and 800 ℃, the sintering time is 5-15h, and then Li is obtained2NiO2Mixing the material with 2-5 wt% nanometer LFP material in an argon protective environment for 5-20h by using a high-energy ball mill to ensure that the nanometer LFP material is mixed in Li2NiO2Then a layer of uniform coating is formed on the surface of the Li-2NiO2@ LFP material.
Example 2
Mixing Li in a molar ratio of 1-1.05:12CO3And FePO4Is prepared from glucose (16%) and Mg (0.5-2%)2(OH)2CO3Taking ethanol as a dispersing agent, ball-milling and mixing for 6-10h, sintering after vacuum drying at 80-100 ℃, wherein the sintering temperature is 700-800 ℃, and the sintering time is 8-12h, so as to obtain the LFP-Mg shell material, and then mixing with 95-98% of Li by mass percent2Ni0.5Cu0.5O2The material is mixed for 5 to 20 hours by a high-energy ball mill to obtain Li2Ni0.5Cu0.5O2@ LFP-Mg material.
Example 3
Mixing Li in a mass ratio of 1.05-1.15:12NiO2@ LFP and LFP are raw materials,wherein Li2NiO @ LFP is used as an additive, LFP is used as a positive active material, 0.5-1% of SP and PVDF are added, NMP is used as a dispersing agent, planetary stirring and mixing are carried out for 3-5h, positive material slurry is prepared, and a high-energy positive material pole piece with the actual density of 2.4-2.5mg/m2 is coated and pressed on an aluminum foil with the thickness of 12 mu m in a transfer coating mode.
Example 4
Preparing a lithium ion battery, namely preparing and winding the high-energy positive electrode material pole piece, the graphite negative electrode and the diaphragm in the embodiment 3 to obtain a naked battery cell, putting the naked battery cell into a shell, injecting liquid, standing at 25 ℃, performing formation, shaping and degassing processes after the electrolyte is soaked to finally obtain the high-energy-density lithium ion battery, and finding that the first efficiency is more than 99% in a formation test stage, as shown in fig. 3.
As shown in fig. 3, the first efficiency of the lithium ion battery containing the Li2NiO2@ LFP additive was > 99% compared to the uncompensated lithium battery.
It is to be noted that the foregoing is only illustrative of the preferred embodiments of the present invention and the technical principles employed. It will be understood by those skilled in the art that the present invention is not limited to the particular embodiments described herein, but is capable of various obvious changes, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore, although the present invention has been described in greater detail by the above embodiments, the present invention is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present invention, and the scope of the present invention is determined by the scope of the appended claims.
Claims (10)
1. A high energy density positive electrode material characterized by: the positive electrode material contains a positive electrode active substance and an additive, and the additive is Li2NixMyO2Core-shell materials of @ LFP-X, i.e. in Li2NixMyO2The exterior of the material is coated with a layer of LFP-X material through physical or chemical coating; wherein x is more than 0 and less than or equal to 1, y is 1-x, M is a metal element such as Cu, Al, Fe, Mn, Co, Ti, Sb, Mg and the like, or B, F and the likeA non-metallic element.
2. The high energy density positive electrode material according to claim 1, wherein: the LFP-X shell material is a pure-phase LiFePO4 material or a pure-phase LiFePO4 metal-doped LFP-X material, wherein X can be Mg, Mn, Al, Ti, V, Nb, Sb and other metals.
3. The high energy density positive electrode material according to claim 1, wherein: the Li2NixMyO2The material @ LFP-X, chemically or physically, Li2NixMyO2The particle size of the @ LFP-X material is 1-10um, wherein Li2NixMyO2The particle size of the core material is 0.5-9.5um, and the particle size of the LFP-X shell material is 0.5-5 um.
4. The high energy density positive electrode material according to claim 3, wherein: the chemical method is a solid phase method or a liquid phase method, and the solid phase method selects a high-temperature solid phase reaction method, a carbothermic reduction method, a microwave synthesis method, a pulse laser deposition method, a sol-gel method, a hydrothermal synthesis method, a precipitation method and a solvothermal synthesis method; the physical method adopts high-energy ball milling and physical vapor deposition.
5. The high energy density positive electrode material according to claim 1, wherein: the Li2NixMyO2The Li source selected in the preparation process of the @ LFP-X material is Li2CO3、LiOH、Li2O、CH3COOLi、LiNO3And Li2C2O4One or more of (1), the iron source is Fe2O3、FeOOH、Fe(OH)3、Fe(NO3)3、Fe2(SO4)3One or more of NiO and NiO as nickel source2、NiOOH、Ni(OH)2、NiNO3、Ni2SO4One or more of metal sources, that is, M is a metal element such as Cu, Al, Fe, Mn, Co, Ti, Sb, Mg, etcWhen element is used, MOx, MO (OH) x, M (NO) are used3)x、M(SO4) x, wherein x depends on the valence state of the metal element.
6. A positive pole piece comprises a metal current collector and a high-energy-density positive pole material, wherein an additive is directly coated on the metal current collector together with a positive active substance, or the micrometer-level thickness additive is sprayed on the pole piece with the positive active substance.
7. The positive electrode sheet according to claim 6, wherein: the mass percentage of the additive to the positive active material is a, and a is more than 0% and less than or equal to 50%.
8. The positive electrode sheet according to claim 6, wherein: the mass percentage of the additive and the positive active material is 5-15%.
9. The positive electrode sheet according to claim 6, wherein: the additive is prepared into slurry, and then is coated on the surface of the positive active material pole piece by a spraying method, a screen printing method and a blade coating method, wherein the thickness of the positive active material pole piece is 1-10 mu m.
10. A lithium ion battery, characterized by: the lithium ion battery comprises a battery shell, a pole core and electrolyte, wherein the pole core and the electrolyte are sealed in the battery shell, the pole core comprises a positive pole, a negative pole and a diaphragm positioned between the positive pole and the negative pole, and the positive pole comprises a positive pole current collector and a high-energy-density positive pole material positioned on the positive pole current collector.
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| CN202210123971.XA CN114725369A (en) | 2022-02-10 | 2022-02-10 | High-energy-density positive electrode material, positive electrode plate and lithium ion battery |
| PCT/CN2022/132003 WO2023151334A1 (en) | 2022-02-10 | 2022-11-15 | High-energy-density positive electrode material, positive electrode sheet and lithium-ion battery |
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| CN202210123971.XA Pending CN114725369A (en) | 2022-02-10 | 2022-02-10 | High-energy-density positive electrode material, positive electrode plate and lithium ion battery |
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| Country | Link |
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| CN (1) | CN114725369A (en) |
| WO (1) | WO2023151334A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023151334A1 (en) * | 2022-02-10 | 2023-08-17 | 中国第一汽车股份有限公司 | High-energy-density positive electrode material, positive electrode sheet and lithium-ion battery |
| WO2024078414A1 (en) * | 2022-10-09 | 2024-04-18 | 深圳市德方创域新能源科技有限公司 | Lithium replenishing additive for positive electrode and preparation method therefor, lithium-rich positive electrode, and secondary battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116936967B (en) * | 2023-09-18 | 2023-12-15 | 江苏正力新能电池技术有限公司 | Lithium supplementing negative electrode piece and lithium battery |
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Also Published As
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| WO2023151334A1 (en) | 2023-08-17 |
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