CN212648280U - Positive pole piece of energy storage device - Google Patents
Positive pole piece of energy storage device Download PDFInfo
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- CN212648280U CN212648280U CN202021939517.4U CN202021939517U CN212648280U CN 212648280 U CN212648280 U CN 212648280U CN 202021939517 U CN202021939517 U CN 202021939517U CN 212648280 U CN212648280 U CN 212648280U
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Abstract
The utility model discloses an energy storage device anode piece, which comprises a current collector and an active material layer, wherein the active material layer is coated on the current collector and comprises an anode active material layer, a first composite material layer and a second composite material layer; the first composite material layer is coated on the outer surface of the positive active material layer and is in a porous net shape; the second composite material layer is coated on the first composite material layer, and the second composite material layer is zirconia particles which are in a porous hollow spherical shape; after the holes in the first composite material layer are communicated with the holes in the second composite material layer, a channel for allowing lithium ions to pass through is formed; the utility model has the advantages that: the side reaction of the electrolyte and the lithium ion positive active material layer is greatly reduced, thereby improving the battery life.
Description
Technical Field
The utility model relates to an energy storage device technical field, more specifically the utility model relates to an energy storage device positive pole piece especially relates to a lithium ion battery positive pole piece.
Background
Lithium batteries include lithium ion batteries and lithium batteries, and the lithium batteries mainly use pure lithium metal as an electrode, and because the lithium metal is relatively active, the lithium batteries have a relatively high risk.
A lithium ion battery is a type of secondary battery that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. During charging and discharging, Li + is inserted and extracted back and forth between two electrodes: during charging, Li + is extracted from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge.
The lithium ion intercalation or deintercalation process completed in the reciprocating process between the two electrodes is realized in the anode material or the cathode material, and the mass ratio of the anode material to the cathode material is 3: 1-4: the performance of the positive pole material directly influences the performance of the lithium ion battery, the cost directly determines the cost of the battery, in the prior art, active materials such as lithium cobaltate, lithium manganate or lithium iron phosphate are generally directly coated with a conductive agent mixed with an adhesive and the like on a current collector to form a positive pole piece, the positive pole piece is placed in the battery to be in direct contact with electrolyte, so that the positive pole material on the positive pole piece is in direct contact with the electrolyte, after multiple charging and discharging, the positive pole material on the positive pole piece can generate side reaction with the electrolyte, and the service life of the battery is shortened.
SUMMERY OF THE UTILITY MODEL
In order to overcome the defects of the prior art, the utility model provides an energy storage device anode piece specifically is a lithium ion battery anode piece, can greatly reduce the side reaction of electrolyte and the positive active material layer of lithium ion to improve the battery life.
The utility model provides a technical scheme that its technical problem adopted is: the improvement of a positive pole piece of an energy storage device is as follows: the current collector comprises a current collector and an active material layer, wherein the active material layer is coated on the current collector and comprises a positive active material layer, a first composite material layer and a second composite material layer;
the first composite material layer is coated on the outer surface of the positive active material layer and is in a porous net shape; the second composite material layer is coated on the first composite material layer, and the second composite material layer is zirconia particles which are in a porous hollow spherical shape;
and after the holes in the first composite material layer are communicated with the holes in the second composite material layer, a channel for allowing lithium ions to pass through is formed.
In the above structure, the positive active material is one of lithium cobaltate, lithium manganate, ternary material and lithium iron phosphate.
In the structure, the diameter of the hole in the first composite material layer is 10-15 nm.
In the above structure, the diameter of the pores in the zirconia particles is 15 to 20 nm.
The utility model has the advantages that: the first composite material layer is provided with a porous reticular structure, the second composite material layer adopts porous hollow spherical zirconium oxide particles, and when the second composite material layer is coated on the surface of the first composite material layer, a channel which only allows lithium ions to pass through can be formed, so that the direct contact between the anode material and the electrolyte is avoided, the side reaction of the electrolyte and the lithium ion anode active material layer is greatly reduced, and the service life of the battery is prolonged.
Drawings
FIG. 1 is a schematic view of the positive electrode plate of the energy storage device of the present invention
Fig. 2 is a schematic structural diagram of an active material layer of a positive electrode plate of an energy storage device according to the present invention.
Fig. 3 is a schematic flow chart of a method for manufacturing a positive electrode plate of an energy storage device according to the present invention.
Detailed Description
The present invention will be further explained with reference to the drawings and examples.
The conception, the specific structure, and the technical effects produced by the present invention will be clearly and completely described below in conjunction with the embodiments and the accompanying drawings to fully understand the objects, the features, and the effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive labor based on the embodiments of the present invention all belong to the protection scope of the present invention. In addition, all the connection/connection relations referred to in the patent do not mean that the components are directly connected, but mean that a better connection structure can be formed by adding or reducing connection auxiliary components according to specific implementation conditions. The utility model discloses each technical feature in the creation can the interactive combination under the prerequisite that does not contradict conflict each other.
As shown in fig. 1 and fig. 2, the utility model discloses an energy storage device positive plate, in particular to a lithium ion battery positive plate, which comprises a current collector 1 and an active material layer 2, wherein the active material layer 2 is coated on the current collector 1, and the active material layer 2 comprises a positive active material layer 10, a first composite material layer 20 and a second composite material layer 30; the positive electrode active material layer 10 is made of a material commonly used in the prior art, for example, one of lithium cobaltate, lithium manganate, a ternary material and lithium iron phosphate, in this embodiment, the positive electrode active material layer 10 is lithium cobaltate, which belongs to a conventional selection manner in the prior art, and therefore, detailed description is not given in this embodiment.
Further, as shown in fig. 2, the first composite material layer 20 covers the outer surface of the positive active material layer 10, and the first composite material layer 20 is in a porous mesh shape, so that the first composite material layer 20 has a plurality of holes, and the diameter of the holes ranges from 10 nm to 15 nm. The first composite material layer 20 wraps the positive electrode active material layer 10, in this embodiment, the first composite material layer 20 is a mixture of aluminum sulfate and phenolic resin glue, and the weight ratio of the aluminum sulfate to the phenolic resin glue is 1: 3, so that the phenolic resin glue can coat the aluminum sulfate to form a porous net-shaped structure; the second composite material layer is coated on the first composite material layer 20, the second composite material layer 30 is zirconia particles, the zirconia particles are in a porous hollow spherical shape, and the diameter of holes in the zirconia particles is 15-20 nm. In this embodiment, after the zirconia particles are combined with the first material composite layer, the pores on the first composite material layer 20 are communicated with the pores on the zirconia, so as to form a passage for lithium ions to pass through.
The utility model discloses a lithium ion battery positive pole piece, first combined material layer 20 in its active material layer forms porous network structure, the second combined material adopts porous cavity spherical zirconia granule, when the cladding of second combined material layer 30 is on first combined material layer 20 surface, can form the passageway that only supplies lithium ion to pass, cathode material and electrolyte direct contact have been avoided, very big reduction the side reaction of electrolyte and the anodal active material layer 10 of lithium ion, thereby the battery life has been improved. Meanwhile, the second composite material layer 30 is formed by zirconia particles, and the zirconia has the advantages of stable high-temperature chemical properties, corrosion resistance, oxidation resistance and the like, and is coated on the outermost layer of the positive active material, so that the service life of the whole positive material can be greatly prolonged. In addition, the first composite material layer 20 is made of a mixture of aluminum sulfate and phenolic resin glue, and the aluminum sulfate is beneficial to forming a solid solution state of the active material, so that crystal lattices are stabilized, and the cycle performance is improved.
Example 1
With reference to fig. 3, the present invention provides a method for manufacturing a positive electrode plate of a lithium ion battery, which includes the following steps:
s1, preparing a coating solution, namely mixing phenolic resin glue, sodium salt and aluminum salt according to the mass ratio of 3: 1: 1, adding the components into a first solvent together, and stirring and mixing to obtain a coating solution; wherein the phenolic resin glue is glue made of phenolic resin, the viscosity range is 4000-5000cps/25 degrees, and the solid content is 20-25 percent; the weight ratio of the phenolic resin glue to the first solvent is 2: 1; s2, preparing a solid-liquid mixture, namely mixing the positive electrode active material and the coating liquid according to the mass ratio of 1: 1, uniformly mixing to obtain a solid-liquid mixture;
s3, first drying and sintering, drying the solid-liquid mixture under the protection of inert gas at the drying temperature of 60 ℃ for 3 hours, and then sintering at the sintering temperature of 500 ℃ for 2 hours to form a first composite material layer 20 on the outer surface of the positive active material;
s4, adding zirconia particles, namely dispersing the sintered substance in the step S3 in a second solvent, adding porous hollow spherical zirconia particles into the second solvent, uniformly mixing, and filtering, wherein the mass ratio of the sintered substance in the step S3 to the second solvent to the zirconia particles is 1: 2: 1;
in this embodiment, the second solvent is water for containing sodium salt, and holes are formed in the first composite material layer 20;
s5, secondary drying and sintering, drying the solid matter obtained by filtering in the step S4 under the protection of inert gas, wherein the drying temperature is 70 ℃, the time is 3 hours, then sintering is carried out, the sintering temperature is 700 ℃, the sintering time is 5 hours, and the sintered material is mixed with an adhesive to prepare an active material;
in this embodiment, the adhesive is a polyvinylidene fluoride adhesive, which is mainly used to firmly fix the sintered material on the current collector, and the viscosity of the polyvinylidene fluoride adhesive is 3000-.
And S6, coating the active material in the S5 on a current collector, drying and rolling to obtain the positive pole piece.
In the above embodiment, the first solvent is ethanol, which is used to dissolve sodium salt, the current collector is an aluminum-plated film, the holes are formed on the first composite material layer 20, and the porous hollow spherical zirconia particles can be coated on the surfaces of the holes to form a channel through which lithium ions can freely pass, thereby reducing the contact between the electrolyte and the positive electrode material and reducing the occurrence of side reactions.
In step S4, the zirconia grains are produced by the following steps:
s41, mixing the zirconium oxide powder and the sodium salt according to the mass ratio of 1: 2 mixing to form a mixture;
and S42, granulating the mixture obtained in the step S41 by using a mixing granulator to form spherical particles with the diameter of 15-20nm, adding the spherical particles into excessive water, and sequentially performing suction filtration and drying to obtain solid particles to obtain the porous hollow spherical zirconium oxide particles.
In the above steps S1 and S41, the sodium salt is one or more of sodium chloride, sodium sulfate, and sodium nitrate. In this example, sodium chloride was used as the sodium salt. And the diameter of the sodium salt is 10-15 nm. In the above step S1, the aluminum salt used is aluminum phosphate or aluminum sulfate, and in this embodiment, the aluminum salt used is aluminum phosphate, and aluminum phosphate is insoluble in methanol or ethanol.
Based on this, the utility model discloses a preparation method of lithium ion battery positive pole piece, first layer combined material is aluminiferous element, the crystal lattice of positive active material has been stabilized, the cycle performance of battery has been improved, spherical porous hollow spherical zirconia of cladding one deck in first combined material outside, the hole above the first layer combined material not only can link together with the hole on the porous spherical zirconia granule of cavity and form the passageway that lithium ion passed jointly, but also can reduce the contact reaction of electrolyte and positive material, the life of improvement battery. In addition, the zirconium oxide has the advantages of stable high-temperature chemical property, corrosion resistance, oxidation resistance and the like, and is coated on the outermost layer of the positive active material, so that the service life of the whole positive material can be greatly prolonged.
Example 2
With reference to fig. 3, the present invention provides a method for manufacturing a positive electrode plate of a lithium ion battery, which includes the following steps:
s1, preparing a coating solution, namely mixing phenolic resin glue, sodium salt and aluminum salt according to the mass ratio of 3: 1: 1, adding the phenolic resin glue and the first solvent together, wherein the weight ratio of the phenolic resin glue to the first solvent is 2: 1, stirring and mixing to obtain a coating solution;
s2, preparing a solid-liquid mixture, namely mixing the positive electrode active material and the coating liquid according to the mass ratio of 1: 1, uniformly mixing to obtain a solid-liquid mixture;
s3, first drying and sintering, drying the solid-liquid mixture under the protection of inert gas, wherein the drying temperature is 90 ℃, the time is 2 hours, then sintering is carried out, the sintering temperature is 800 ℃, the time is 1 hour, and a first composite material layer 20 is formed on the outer surface of the positive active material;
s4, adding zirconia particles, namely dispersing the sintered substance in the step S3 in a second solvent, adding porous hollow spherical zirconia particles into the second solvent, uniformly mixing, and filtering, wherein the mass ratio of the sintered substance in the step S3 to the second solvent to the zirconia particles is 1: 2: 1;
in this embodiment, the second solvent is water for containing sodium salt, and holes are formed in the first composite material layer 20;
and S5, secondary drying and sintering, drying the solid matter obtained by filtering in the step S4 under the protection of inert gas, wherein the drying temperature is 80 ℃, the time is 2 hours, then sintering is carried out, the sintering temperature is 900 ℃, the sintering time is 3 hours, and the sintered material is mixed with an adhesive to obtain the active material.
In this embodiment, the adhesive is a polyvinylidene fluoride adhesive, which is mainly used to firmly fix the sintered material on the current collector, and the viscosity of the polyvinylidene fluoride adhesive is 3000-.
And S6, coating the active material in the S5 on a current collector, drying and rolling to obtain the positive pole piece.
In the above embodiment, the first solvent is ethanol, which is used to dissolve sodium salt, the current collector is an aluminum-plated film, the holes are formed on the first composite material layer 20, and the porous hollow spherical zirconia particles can be coated on the surfaces of the holes to form a channel through which lithium ions can freely pass, thereby reducing the contact between the electrolyte and the positive electrode material and reducing the occurrence of side reactions.
In step S4, the zirconia grains are produced by the following steps:
s41, mixing the zirconium oxide powder and the sodium salt according to the mass ratio of 1: 2 mixing to form a mixture;
and S42, granulating the mixture obtained in the step S41 by using a mixing granulator to form spherical particles with the diameter of 15-20nm, adding the spherical particles into excessive water, and sequentially performing suction filtration and drying to obtain solid particles to obtain the porous hollow spherical zirconium oxide particles.
In the above steps S1 and S41, the sodium salt is one or more of sodium chloride, sodium sulfate, and sodium nitrate. In this example, sodium chloride was used as the sodium salt. And the diameter of the sodium salt is 10-15 nm. In the above step S1, the aluminum salt used is aluminum phosphate or aluminum sulfate, and in this embodiment, the aluminum salt used is aluminum phosphate, and aluminum phosphate is insoluble in methanol or ethanol.
Based on this, the utility model discloses a preparation method of lithium ion battery positive pole piece, first layer combined material is aluminiferous element, the crystal lattice of positive active material has been stabilized, the cycle performance of battery has been improved, spherical porous hollow spherical zirconia of cladding one deck in first combined material outside, the hole above the first layer combined material not only can link together with the hole on the porous spherical zirconia granule of cavity and form the passageway that lithium ion passed jointly, but also can reduce the contact reaction of electrolyte and positive material, the life of improvement battery. In addition, the zirconium oxide has the advantages of stable high-temperature chemical property, corrosion resistance, oxidation resistance and the like, and is coated on the outermost layer of the positive active material, so that the service life of the whole positive material can be greatly prolonged.
Example 3
With reference to fig. 3, the present invention provides a method for manufacturing a positive electrode plate of a lithium ion battery, which includes the following steps:
s1, preparing a coating solution, namely mixing phenolic resin glue, sodium salt and aluminum salt according to the mass ratio of 3: 1: 1, adding the phenolic resin glue and the first solvent together, wherein the weight ratio of the phenolic resin glue to the first solvent is 2: 1, stirring and mixing to obtain a coating solution;
s2, preparing a solid-liquid mixture, namely mixing the positive electrode active material and the coating liquid according to the mass ratio of 1: 1, uniformly mixing to obtain a solid-liquid mixture;
s3, first drying and sintering, drying the solid-liquid mixture under the protection of inert gas, wherein the drying temperature is 75 ℃, the time is 2.5h, then sintering is carried out, the sintering temperature is 650 ℃, the time is 1.5h, and a first composite material layer 20 is formed on the outer surface of the positive active material;
s4, adding zirconium oxide particles, namely dispersing the sintered substance in the step S3 in a second solvent, adding porous hollow spherical zirconium oxide particles into the second solvent, uniformly mixing and filtering; wherein the mass ratio of the sintered substance, the second solvent and the zirconia particles in step S3 is 1: 2: 1;
in this embodiment, the second solvent is water for containing sodium salt, and holes are formed in the first composite material layer 20;
s5, secondary drying and sintering, drying the solid matter obtained by filtering in the step S4 under the protection of inert gas, wherein the drying temperature is 75 ℃, the time is 2.5 hours, then sintering is carried out, the sintering temperature is 800 ℃, the sintering time is 4 hours, and the sintered material is mixed with an adhesive to prepare an active material;
in this embodiment, the adhesive is a polyvinylidene fluoride adhesive, which is mainly used to firmly fix the sintered material on the current collector, and the viscosity of the polyvinylidene fluoride adhesive is 3000-.
And S6, coating the active material in the S5 on a current collector, drying and rolling to obtain the positive pole piece.
In the above embodiment, the first solvent is ethanol, which is used to dissolve sodium salt, the current collector is an aluminum-plated film, the holes are formed on the first composite material layer 20, and the porous hollow spherical zirconia particles can be coated on the surfaces of the holes to form a channel through which lithium ions can freely pass, thereby reducing the contact between the electrolyte and the positive electrode material and reducing the occurrence of side reactions.
In step S4, the zirconia grains are produced by the following steps:
s41, mixing the zirconium oxide powder and the sodium salt according to the mass ratio of 1: 2 mixing to form a mixture;
and S42, granulating the mixture obtained in the step S41 by using a mixing granulator to form spherical particles with the diameter of 15-20nm, adding the spherical particles into excessive water, and sequentially performing suction filtration and drying to obtain solid particles to obtain the porous hollow spherical zirconium oxide particles.
In the above steps S1 and S41, the sodium salt is one or more of sodium chloride, sodium sulfate, and sodium nitrate. In this example, sodium chloride was used as the sodium salt. And the diameter of the sodium salt is 10-15 nm. In the above step S1, the aluminum salt used is aluminum phosphate or aluminum sulfate, and in this embodiment, the aluminum salt used is aluminum sulfate, and aluminum sulfate is insoluble in methanol or ethanol.
Based on this, the utility model discloses a preparation method of energy storage device positive pole piece, first layer combined material is aluminiferous element, the crystal lattice of positive active material has been stabilized, the cycle performance of battery has been improved, spherical porous hollow spherical zirconia of one deck is wrapped to first combined material outside, the hole above the first layer combined material not only can link together with the hole on the porous spherical zirconia granule of cavity and form the passageway that lithium ion passed jointly, but also can reduce the contact reaction of electrolyte and positive material, the life of improvement battery. In addition, the zirconium oxide has the advantages of stable high-temperature chemical property, corrosion resistance, oxidation resistance and the like, and is coated on the outermost layer of the positive active material, so that the service life of the whole positive material can be greatly prolonged.
Based on foretell embodiment, the utility model also provides a lithium ion battery, including positive pole piece, negative pole piece and electrolyte, positive pole piece include by the lithium ion battery positive pole piece that makes in an arbitrary embodiment.
In addition, the present invention also provides a method for testing the service life of the battery, wherein the lithium ion batteries in example 1 and example 2 of the following table are prepared as follows: the positive pole piece adopts the positive pole piece of the lithium ion battery, and the negative pole piece consists of negative conductive agent conductive graphite, negative adhesive styrene butadiene rubber and negative current collector copper foil; the electrolyte consists of lithium salt LiBF4, solvent dimethyl carbonate and additive fluoroethylene carbonate; and then, preparing the lithium ion battery according to a normal lithium ion battery production process.
The lithium batteries employed in comparative examples 1 and 2 of the following table are different from the lithium batteries in examples 1 and 2 in that the outer surface of the positive electrode active material layer 10 on the positive electrode tab active material is not coated with the first composite material layer 20 and the second composite material layer 30.
Assembling a positive pole piece, a negative pole piece and a coating diaphragm into a button battery in an argon-filled glove box, and performing battery capacity cycle test on a cycle charge-discharge tester, wherein the specific data are as follows:
combine the data of table above, can see, no matter be the capacity before the circulation charge, still the capacity of circulation charge volume, through adopting the utility model discloses a lithium ion battery that the preparation method of lithium ion battery positive pole piece made all compares not adopting the utility model discloses a lithium ion battery that preparation method made is great, and the capacity retention rate is also better relatively.
While the preferred embodiments of the present invention have been described, the present invention is not limited to the above embodiments, and those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention, and such equivalent modifications or substitutions are intended to be included within the scope of the present invention as defined by the appended claims.
Claims (4)
1. The utility model provides an energy storage device positive pole piece which characterized in that: the current collector comprises a current collector body and an active material layer, wherein the active material layer is coated on the current collector body and comprises a positive active material layer, a first composite material layer and a second composite material layer;
the first composite material layer is coated on the outer surface of the positive active material layer and is in a porous net shape; the second composite material layer is coated on the first composite material layer, and the second composite material layer is zirconia particles which are in a porous hollow spherical shape;
and after the holes in the first composite material layer are communicated with the holes in the second composite material layer, a channel for allowing lithium ions to pass through is formed.
2. The positive electrode sheet of an energy storage device as claimed in claim 1, wherein: the positive active material is one of lithium cobaltate, lithium manganate, ternary material and lithium iron phosphate.
3. The positive electrode sheet of an energy storage device as claimed in claim 1, wherein: the diameter of the hole in the first composite material layer is 10-15 nm.
4. The positive electrode sheet of an energy storage device as claimed in claim 1, wherein: the diameter of the holes on the zirconia particles is 15-20 nm.
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