CN113066960A - Double-composite modified spinel lithium manganate positive plate and preparation method thereof - Google Patents
Double-composite modified spinel lithium manganate positive plate and preparation method thereof Download PDFInfo
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- 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
- H01M4/50—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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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention discloses a double-composite modified spinel lithium manganate positive plate, which consists of a spinel lithium manganate substrate, a lithium manganese phosphate coating and an inorganic solid electrolyte coating; or consists of a spinel lithium manganate substrate, an inorganic solid electrolyte coating and a lithium iron manganese phosphate coating; or consists of a spinel lithium manganate substrate and a composite coating, wherein the composite coating is a composite coating consisting of lithium manganese iron phosphate, an inorganic solid electrolyte and a binder; in the positive plate, the mass of the spinel lithium manganate is 6-9 parts by mass, the mass of the lithium manganese iron phosphate is 1-4 parts by mass, and the mass of the inorganic solid electrolyte is 0.3-3% of the total mass of the spinel lithium manganate and the lithium manganese iron phosphate. The invention also discloses a preparation method of the double-composite modified spinel lithium manganate positive plate and a lithium ion battery prepared from the double-composite modified spinel lithium manganate positive plate. The double-composite modified spinel lithium manganate positive plate disclosed by the invention is low in cost and easy for large-scale production, and can improve the performance of a lithium manganate battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a double-composite modified spinel lithium manganate positive plate, a preparation method thereof and a lithium ion battery.
Background
Spinel lithium manganate material (LiMn)2O4) The lithium battery anode material has the advantages of high discharge platform, good low-temperature performance, low cost, rich manganese raw materials, less environmental pollution, simple preparation process and the like, and has good application prospect. The battery has the advantages that two working voltage platforms of 3V and 4V are arranged in the charging and discharging process, the spinel structure generates Jahn-Teller effect on the 3V voltage platform, phase transformation exists in the battery charging and discharging process, the cubic phase is transformed into the tetragonal phase, the structural stability is poor, the material structure is distorted, the lithium ion deintercalation channel is blocked, and high-concentration Mn is generated in the final stage of discharging3+Disproportionation reaction on the particle surface to produce Mn2+Dissolving in electrolyte; particularly, at high temperature, hydrofluoric acid decomposed by lithium hexafluorophosphate plays a role in catalysis, and manganese dissolution is accelerated, so that spinel LiMn is reduced2O4The charge-discharge specific capacity and the cycling stability of the battery.
The lithium iron manganese phosphate material has a stable olivine structure, does not change in the structure in the lithium ion de-intercalation process, and has good high-temperature cycle performance. Therefore, by means of doping and cladding, lithium iron manganese phosphate is adopted to modify the spinel lithium manganate material, and the cycle performance of the spinel lithium manganate can be improved.
The Chinese patent with publication number CN104134815A discloses a mixed anode material and application, wherein two substances of lithium manganate and lithium manganese iron phosphate are mixed to serve as an anode active material, the method improves the cycle and safety performance, but the particle size of the lithium manganese iron phosphate is large, the lithium ion deintercalation is influenced, the pole piece compaction is reduced, and the improvement effect is limited. The chinese patent publication No. CN105552431A discloses a graphene-doped high-energy lithium iron phosphate battery, in which the positive active material includes lithium iron phosphate, lithium manganate or lithium manganese iron phosphate, and the method does not show significant performance improvement, and the specific capacity and compaction do not meet the common knowledge in the industry. The Chinese patent with publication number CN108232174A discloses a positive active material, a lithium ion battery and a preparation method thereof, wherein the positive active material comprises 6-8 parts by mass of 532-type ternary material, 1-3 parts by mass of lithium manganese iron phosphate and 1-3 parts by mass of lithium manganate.
Chinese patent publication No. CN 109417162 a discloses a method for preparing a positive electrode sheet, in which a positive electrode material includes at least one of a nickel-cobalt-manganese ternary material, a nickel-cobalt-aluminum ternary material, lithium nickel manganese oxide, lithium manganese oxide, and lithium cobaltate, lithium manganese iron phosphate and an organic solvent are made into an additive, mixed with the positive electrode material, a conductive agent, and a binder to obtain a positive electrode slurry, and then coated on an aluminum foil to obtain the positive electrode sheet. The method also does not solve the problem of uniform distribution of the slurry of the lithium manganese iron phosphate and the anode material, and the coating amount of the used lithium manganese iron phosphate carbon is 10-40%, and the carbon content is too high, so that the performance of the lithium manganese iron phosphate material can be prevented from being exerted.
Therefore, a new method for applying lithium iron manganese phosphate and lithium manganate to the positive plate is needed to overcome the technical problems and the cost problems, and obtain the composite positive plate which has excellent performance, low cost and easy large-scale production.
Disclosure of Invention
The invention aims to provide a preparation method of a double-composite modified spinel lithium manganate positive plate and a lithium ion battery.
The invention provides a double-composite modified spinel lithium manganate positive plate, which consists of a spinel lithium manganate substrate, a lithium manganese phosphate coating and an inorganic solid electrolyte coating, wherein the lithium manganese phosphate coating and the inorganic solid electrolyte coating are sequentially coated on the spinel lithium manganate substrate;
or the positive plate consists of a spinel lithium manganate substrate, an inorganic solid electrolyte coating and a lithium manganese iron phosphate coating which are sequentially coated on the spinel lithium manganate substrate;
or the positive plate consists of a spinel lithium manganate substrate and a composite coating coated on the spinel lithium manganate substrate, wherein the composite coating is a composite coating consisting of lithium manganese iron phosphate, an inorganic solid electrolyte and a binder;
in the positive plate, the mass of the spinel lithium manganate is 6-9 parts by mass, the mass of the lithium manganese iron phosphate is 1-4 parts by mass, and the mass of the inorganic solid electrolyte is 0.3-3% of the total mass of the spinel lithium manganate and the lithium manganese iron phosphate.
Preferably, the positive plate comprises 7-8 parts by mass of spinel lithium manganate and 2-3 parts by mass of lithium manganese iron phosphate.
In the invention, the spinel lithium manganate is capacity type lithium manganate D509 to 18 μm; or the spinel lithium manganate is single crystal lithium manganate D506 to 12 μm.
In the invention, the molecular formula of the lithium manganese iron phosphate is LiMnxFe1-xPO4Wherein 0 is<x<1. Preferably, the lithium manganese iron phosphate is LiMn0.5Fe0.5PO4、LiMn0.6Fe0.4PO4、LiMn0.7Fe0.3PO4、LiMn0.8Fe0.2PO4、LiMn0.9Fe0.1PO4One kind of (1). Preferably, D of the lithium iron manganese phosphate50100-500 nm, and electron conductivity greater than 10-3S/cm。
In the positive plate material, small-particle lithium manganese iron phosphate and large-particle spinel lithium manganate jointly form an active substance of the positive plate, and the mass ratio of the small-particle lithium manganese iron phosphate to the large-particle spinel lithium manganate is preferably 1: 2-1: 10.
In the invention, the mass of the inorganic solid electrolyte is 0.3-3% of that of active substances (spinel lithium manganate and lithium manganese iron phosphate). If the content of the inorganic solid electrolyte is too low, the effect of constructing a lithium ion fast channel is not obtained, and if the content is too high, the active material is reducedThe amount of (A) to (B). D of the inorganic solid electrolyte50Preferably 50 to 300nm, the smaller the particle size, the easier the connection of the active material, but the smaller the particle size, difficult to disperse, high preparation cost, and the use of mature sand mill for nano-crystallization is easy to reach 50 to 300nm size. The inorganic solid electrolyte may employ an inorganic solid electrolyte commonly used in the art, and is preferably one of Lithium Aluminum Titanium Phosphate (LATP), Lithium Lanthanum Titanate (LLTO), and Lithium Lanthanum Zirconium Oxide (LLZO).
In the invention, the conductive agent can be selected from conductive agents commonly used in the field, and is preferably one or a mixture of more than two of carbon black conductive agent (sp), graphite conductive agent and Carbon Nanotubes (CNTs). The binder can be selected from binders commonly used in the art, preferably polyvinylidene fluoride (PVDF).
The double-composite modified spinel lithium manganate positive plate can be prepared by the following steps:
s1, mixing spinel lithium manganate, a conductive agent and a binder by a dry method, adding N-methylpyrrolidone (NMP), and stirring to form a viscous paste; adding N-methyl pyrrolidone, and stirring at a high rotation speed to obtain a slurry A; coating the slurry A on a current collector, and drying to obtain a spinel lithium manganate substrate;
s2, sanding the lithium manganese iron phosphate, the binder and the N-methyl pyrrolidone together to enable the raw materials to be nano-sized to obtain slurry B;
or sanding the inorganic solid electrolyte, the binder and the N-methyl pyrrolidone together to make the raw materials into nano-sized particles to obtain slurry C;
or sanding the lithium manganese iron phosphate, the inorganic solid electrolyte, the binder and the N-methyl pyrrolidone together to enable the raw materials to be nano-sized, so as to obtain slurry D;
s3, coating the slurry B on the spinel lithium manganate substrate, drying, coating the slurry C again, and drying;
or coating the slurry C on the spinel lithium manganate substrate, drying, coating the slurry B again, and drying;
or coating the slurry D on the spinel lithium manganate substrate and drying;
and S4, rolling to obtain the double-composite modified spinel lithium manganate positive plate.
In the preparation steps, the solid substances are mixed by a dry method and prepared into a pasty mixture, and the main purpose is to ensure that the positive electrode material, the conductive agent and the binder are fully dispersed and avoid agglomeration; by respectively preparing the lithium manganese iron phosphate and the inorganic solid electrolyte into slurry for coating, the agglomeration of the nanoscale lithium manganese iron phosphate and the inorganic solid electrolyte material can be better prevented.
In the above steps, the preparation of the positive plate can adopt one of extrusion coating, transfer coating, micro-gravure coating and blade coating.
In the above step, the solid contents of the slurries a to D are preferably 50% to 70%.
In the step S1, the viscosity of the slurry A is preferably 10000-30000 mpa.s, and the coating surface density is preferably 150-300 g/m2(ii) a In the step S2, the viscosity of the slurry B and the viscosity of the slurry C are preferably 5000-10000 mpa.s, and the viscosity of the slurry D is preferably 8000-10000 mpa.s. The coating thickness is preferably 1 to 2 μm.
In the step S4, the compacted density after rolling is preferably 3.1-3.4 g/cm3。
The invention also provides a lithium ion battery which comprises a positive plate, a negative plate, electrolyte and a diaphragm, wherein the positive plate is the double-composite modified spinel lithium manganate positive plate.
Preferably, the electrolyte is an organic electrolyte.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. according to the invention, a submicron lithium iron manganese phosphate cathode material and an inorganic solid electrolyte are first subjected to nanocrystallization creatively and then mixed with spinel lithium manganate for use, and the characteristics of high electronic conductivity, low internal resistance and high ionic conductivity of the nano inorganic solid electrolyte of the lithium iron manganese phosphate in a nanostructure are utilized to be compounded with the spinel lithium manganate, so that the polarization and manganese dissolution of the lithium manganate are reduced, and the cycle performance is improved.
2. According to the invention, the problem that segregation occurs in the material mixing process due to different densities of lithium manganese iron phosphate and the spinel lithium manganate anode material is solved by a step-by-step coating and one-step rolling method, and the inorganic solid electrolyte coating is introduced, so that a high-speed ion and electron double-transmission channel is established, the compaction density is improved, and the contact between active substances is further improved.
3. The invention adopts different preparation methods simultaneously, can fully exert the synergistic effect of the lithium iron manganese phosphate, the inorganic solid electrolyte and the spinel lithium manganate, also solves the problem of agglomeration of nano-grade materials, can better construct a lithium ion channel and improve the cycle performance.
Drawings
FIG. 1 is a flow chart of the preparation process of the double-composite modified spinel lithium manganate positive plate of the present invention.
Fig. 2 is a graph comparing the cycle life of square aluminum cell prepared in example 1 and comparative example 1.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
Example 1
4kg of lithium manganate, 0.06kg of sp, 0.09kg of CNTs and 0.2kg of PVDF were put into a 10L planetary mixer, wherein the lithium manganate was a volumetric lithium manganate D50The particle size was 15 μm. The stirrer revolves for 30r/min and is stirred for 0.5h, 1kg of NMP is added, then the rotation speed is opened for 1000r/min and the stirring is carried out for 1h, and the mixed materials are made into thick paste; then adding 1kg of NMP, raising the revolution to 35r/min, opening a dispersion disc, gradually raising the rotation speed to 3500r/min at 1000r/min, stirring at high speed for 2h, and finally adding 0.3kg of NMP to adjust the viscosity to obtain uniform anode slurry A with the viscosity of 10100 mpa.s. Coating the slurry A on an aluminum foil with the thickness of 15 mu m and drying, wherein the coating surface density is 230g/m2I.e. the substrate.
Adding 1kg of lithium manganese iron phosphate, 0.1kg of LATP, 0.14kg of PVDF and 1.4kg of NMP into a sand mill, wherein the lithium manganese iron phosphate is LiMn0.8Fe0.2PO4，D50The particle size is 1.3 mu m, the diameter of the zirconia ball is 0.3mm, the mass ratio of the zirconia ball to the material is 10:1, the rotational speed of a sand mill is 2000r/min, the grinding time is 10min, and slurry D with the viscosity of 6000mpa.s is obtained; slurry D was coated onto a substrate to a thickness of 2 μm.
Tabletting by using a roller press to ensure that the compacted density of the pole piece is 3.1g/cm3And obtaining the double-composite modified spinel lithium manganate positive plate.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 22.3Ah, and the battery has the residual capacity of 19.9Ah after being cycled for 460 times at normal temperature.
Example 2
The substrate was prepared in the same manner as in example 1.
Adding 1kg of lithium manganese iron phosphate, 0.1kg of LLTO, 0.14kg of PVDF and 1.4kg of NMP into a sand mill, wherein the lithium manganese iron phosphate is LiMn0.6Fe0.4PO4，D50The particle size is 1.1 mu m, the diameter of the zirconia ball is 0.3mm, the mass ratio of the zirconia ball to the material is 10:1, the rotation speed of a sand mill is 2000r/min, the grinding time is 10min, and slurry D with the viscosity of 7000mpa.s is obtained; slurry D was coated onto a substrate to a thickness of 2 μm.
Tabletting by using a roller press to ensure that the compacted density of the pole piece is 3.1g/cm3And obtaining the double-composite modified spinel lithium manganate positive plate.
Example 3
The substrate was prepared as in example 1.
Adding 1kg of lithium manganese iron phosphate, 0.14kg of PVDF and 1.4kg of NMP into a sand mill, wherein the lithium manganese iron phosphate is LiMn0.8Fe0.2PO4，D50The particle size is 1.3 mu m, the diameter of the zirconia ball is 0.3mm, the mass ratio of the zirconia ball to the materials is 10:1, the rotation speed of a sand mill is 2000r/min, the grinding time is 10min, and slurry B is obtained, wherein the viscosity is 11000 mpa.s; slurry B was coated onto a substrate to a thickness of 1 μm.
Adding 0.1kg of LATP, 0.02kg of PVDF and 0.2kg of NMP into a sand mill, wherein lithium iron manganese phosphate is LiMn0.6Fe0.4PO4，D50Particle sizeThe particle size is 1.1 mu m, the diameter of the zirconia ball is 0.3mm, the mass ratio of the zirconia ball to the materials is 10:1, the rotation speed of a sand mill is 2000r/min, the grinding time is 10min, and slurry C with the viscosity of 7000mpa.s is obtained; slurry C was coated on a substrate formed of slurry B to a thickness of 1 μm.
Tabletting by using a roller press to ensure that the compacted density of the pole piece is 3.2g/cm3And obtaining the double-composite modified spinel lithium manganate positive plate.
Example 4
The substrate was prepared as in example 1.
Adding 1kg of lithium manganese iron phosphate, 0.14kg of PVDF and 1.4kg of NMP into a sand mill, wherein the lithium manganese iron phosphate is LiMn0.6Fe0.4PO4，D50The particle size is 1.1 mu m, the diameter of the zirconia ball is 0.3mm, the mass ratio of the zirconia ball to the material is 10:1, the rotation speed of a sand mill is 2000r/min, the grinding time is 10min, and slurry B is obtained, and the viscosity is 13000 mpa.s.
Adding 0.1kg of LLTO, 0.02kg of PVDF and 0.2kg of NMP into a sand mill, wherein the diameter of a zirconia ball is 0.3mm, the mass ratio of the zirconia ball to the materials is 10:1, the rotating speed of the sand mill is 2000r/min, the grinding time is 10min, and slurry C with the viscosity of 9000mpa.s is obtained.
The slurry C was coated on the substrate to a thickness of 2 μm, and then the slurry B was coated to a thickness of 1 μm.
Tabletting by using a roller press to ensure that the compacted density of the pole piece is 3.2g/cm3And obtaining the double-composite modified spinel lithium manganate positive plate.
Comparative example 1
The substrate was prepared as in example 1.
Adding 1kg of lithium manganese iron phosphate, 0.14kg of PVDF and 1.4kg of NMP into a sand mill, wherein the lithium manganese iron phosphate is LiMn0.8Fe0.2PO4，D50The particle size is 1.3 mu m, the diameter of the zirconia ball is 0.3mm, the mass ratio of the zirconia ball to the materials is 10:1, the rotation speed of a sand mill is 2000r/min, the grinding time is 10min, and slurry B is obtained, and the viscosity is 8000 mpa.s; slurry B was coated onto a substrate to a thickness of 2 μm.
Tabletting by using a roller press to ensure that the pole piece compaction density is 3.1 g/mlcm3And obtaining the double-composite modified spinel lithium manganate positive plate.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 22.6Ah, and 17.57Ah capacity remains after the battery is cycled for 600 times at normal temperature.
Comparative example 2
The substrate was prepared in the same manner as in example 1.
Slurry C was prepared as in example 3, with a coating thickness of 2 μm.
Tabletting by using a roller press to ensure that the compacted density of the pole piece is 3.2g/cm3And obtaining the double-composite modified spinel lithium manganate positive plate.
The capacity retention rate of the lithium ion battery prepared in example 1 after 460 cycles at normal temperature exceeds 89%; the capacity retention rate of the lithium ion battery prepared in the comparative example 1 after 600 times of normal temperature circulation is only 77%; and as shown in fig. 2, the normal temperature cycle performance of the lithium ion battery prepared in comparative example 1 is significantly lower than that of the lithium ion battery prepared in example 1.
Therefore, the double-composite modified spinel lithium manganate positive plate is beneficial to improving the cycle performance of a lithium manganate battery.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A double-composite modified spinel lithium manganate positive plate is characterized in that,
the positive plate consists of a spinel lithium manganate substrate, a lithium iron manganese phosphate coating and an inorganic solid electrolyte coating, wherein the lithium iron manganese phosphate coating and the inorganic solid electrolyte coating are sequentially coated on the spinel lithium manganate substrate;
or the positive plate consists of a spinel lithium manganate substrate, an inorganic solid electrolyte coating and a lithium manganese iron phosphate coating which are sequentially coated on the spinel lithium manganate substrate;
or the positive plate consists of a spinel lithium manganate substrate and a composite coating coated on the spinel lithium manganate substrate, wherein the composite coating is a composite coating consisting of lithium manganese iron phosphate, an inorganic solid electrolyte and a binder;
in the positive plate, the mass of the spinel lithium manganate is 6-9 parts by mass, the mass of the lithium manganese iron phosphate is 1-4 parts by mass, and the mass of the inorganic solid electrolyte is 0.3-3% of the total mass of the spinel lithium manganate and the lithium manganese iron phosphate.
2. The double-composite modified spinel lithium manganate positive electrode sheet of claim 1, wherein said spinel lithium manganate is a capacity type lithium manganate, D509 to 18 μm; or the spinel lithium manganate is single crystal lithium manganate D506 to 12 μm.
3. The double-composite modified spinel lithium manganate positive plate of claim 1, wherein said lithium iron manganese phosphate is LiMn0.5Fe0.5PO4、LiMn0.6Fe0.4PO4、LiMn0.7Fe0.3PO4、LiMn0.8Fe0.2PO4、LiMn0.9Fe0.1PO4One kind of (1).
4. The double-composite modified spinel lithium manganate positive plate of claim 3, wherein D of said lithium iron manganese phosphate50100-500 nm, and electron conductivity greater than 10-3S/cm。
5. The dual composite modified spinel lithium manganate positive plate of claim 1, wherein said inorganic solid electrolyte is one of lithium aluminum titanium phosphate, lithium lanthanum titanate, lithium lanthanum zirconium oxide, D50Is 50 to 300 nm.
6. The preparation method of the double-composite modified spinel lithium manganate positive plate according to any one of claims 1 to 5, characterized by comprising the following steps:
s1, mixing spinel lithium manganate, a conductive agent and a binder by a dry method, adding N-methyl pyrrolidone, and stirring to form a viscous paste; adding N-methyl pyrrolidone, and stirring at a high rotation speed to obtain a slurry A; coating the slurry A on a current collector, and drying to obtain a spinel lithium manganate substrate;
s2, sanding the lithium manganese iron phosphate, the binder and the N-methyl pyrrolidone together to enable the raw materials to be nano-sized to obtain slurry B;
or sanding the inorganic solid electrolyte, the binder and the N-methyl pyrrolidone together to make the raw materials into nano-sized particles to obtain slurry C;
or sanding the lithium manganese iron phosphate, the inorganic solid electrolyte, the binder and the N-methyl pyrrolidone together to enable the raw materials to be nano-sized, so as to obtain slurry D;
s3, coating the slurry B on the spinel lithium manganate substrate, drying, coating the slurry C again, and drying;
or coating the slurry C on the spinel lithium manganate substrate, drying, coating the slurry B again, and drying;
or coating the slurry D on the spinel lithium manganate substrate and drying;
and S4, rolling to obtain the double-composite modified spinel lithium manganate positive plate.
7. The preparation method of the double-composite modified spinel lithium manganate positive plate of claim 6, wherein the solid content of each of the slurries A-D is 50-70%.
8. The preparation method of the double-composite modified spinel lithium manganate positive electrode sheet according to claim 6, characterized in that, in step S1, the viscosity of slurry A is 10000-30000 mpa.s, and the coating surface density is 150-300 g/m2；
In step S2, the viscosity of the slurry B and the slurry C is 5000-10000 mpa.s, the viscosity of the slurry D is 8000-10000 mpa.s, and the coating thickness is 1-2 μm.
9. The preparation method of the double-composite modified spinel lithium manganate positive electrode sheet according to claim 6, characterized in that in step S4, the compacted density after rolling is 3.1-3.4 g/cm3。
10. A lithium ion battery, which comprises a positive plate, a negative plate, electrolyte and a diaphragm, and is characterized in that the positive plate is the double-composite modified spinel lithium manganate positive plate of any one of claims 1 to 5.
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| CN113594413A (en) * | 2021-08-10 | 2021-11-02 | 星恒电源股份有限公司 | Positive plate for balancing lithium ion diffusion and lithium ion battery |
| CN113594412A (en) * | 2021-08-10 | 2021-11-02 | 星恒电源股份有限公司 | Lithium battery positive plate with sandwich structure and lithium battery |
| CN113636532A (en) * | 2021-08-10 | 2021-11-12 | 星恒电源股份有限公司 | Modified lithium iron manganese phosphate cathode material, preparation method thereof and lithium ion battery |
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| CN113594413A (en) * | 2021-08-10 | 2021-11-02 | 星恒电源股份有限公司 | Positive plate for balancing lithium ion diffusion and lithium ion battery |
| CN113594412A (en) * | 2021-08-10 | 2021-11-02 | 星恒电源股份有限公司 | Lithium battery positive plate with sandwich structure and lithium battery |
| CN113636532A (en) * | 2021-08-10 | 2021-11-12 | 星恒电源股份有限公司 | Modified lithium iron manganese phosphate cathode material, preparation method thereof and lithium ion battery |
| CN113823765A (en) * | 2021-08-10 | 2021-12-21 | 星恒电源股份有限公司 | Lithium manganate/lithium manganese iron phosphate composite positive plate and lithium ion battery |
| CN113823765B (en) * | 2021-08-10 | 2022-12-23 | 星恒电源股份有限公司 | Lithium manganate/lithium manganese iron phosphate composite positive plate and lithium ion battery |
| CN113594413B (en) * | 2021-08-10 | 2024-04-26 | 星恒电源股份有限公司 | Positive plate for balancing lithium ion diffusion and lithium ion battery |
| CN113839097A (en) * | 2021-08-24 | 2021-12-24 | 浙江超恒动力科技有限公司 | Preparation method of electric bicycle battery |
| CN113839097B (en) * | 2021-08-24 | 2023-10-24 | 浙江超恒动力科技有限公司 | Preparation method of electric bicycle battery |
| CN115360326A (en) * | 2022-10-21 | 2022-11-18 | 清陶(昆山)能源发展股份有限公司 | Composite anode and lithium ion battery |
| CN116632191A (en) * | 2023-05-17 | 2023-08-22 | 孚能科技(赣州)股份有限公司 | Modified lithium iron manganese phosphate positive electrode material, preparation method thereof and lithium ion battery |
| CN116632191B (en) * | 2023-05-17 | 2024-04-09 | 孚能科技(赣州)股份有限公司 | Modified lithium iron manganese phosphate positive electrode material, preparation method thereof and lithium ion battery |
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