CN112164788A - Lithium ion battery and preparation method thereof - Google Patents

Lithium ion battery and preparation method thereof Download PDF

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Publication number
CN112164788A
CN112164788A CN202011055059.2A CN202011055059A CN112164788A CN 112164788 A CN112164788 A CN 112164788A CN 202011055059 A CN202011055059 A CN 202011055059A CN 112164788 A CN112164788 A CN 112164788A
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electrolyte
lithium ion
ion battery
diaphragm
battery
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郑正坤
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Dongguan Lilong Battery Technology Co ltd
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Dongguan Lilong Battery Technology Co ltd
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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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a lithium ion battery, which comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate and electrolyte; the active substance of the positive plate comprises a nano nickel-based Prussian blue material; the active substance of the negative plate comprises a graphite material with the surface subjected to carbon coating treatment; the diaphragm is a polyolefin film coated with a ceramic material on the surface; the electrolyte is an electrolyte with low-temperature performance. Compared with the prior art, the battery provided by the invention takes the nano nickel-based Prussian blue material as the positive electrode and the carbon-coated graphite material as the negative electrode, and the battery core is prepared by the nano nickel-based Prussian blue material and the diaphragm coated with the ceramic material on the surface and is placed in the electrolyte with low-temperature performance to perform combined action, so that the battery still has reversible charge and discharge performance and excellent capacity retention rate at ultralow temperature of-70 ℃, and the safety performance of the battery is ensured.

Description

Lithium ion battery and preparation method thereof
Technical Field
The invention relates to the field of lithium batteries, in particular to a lithium ion battery and a preparation method thereof.
Background
Conventionally used lithium ion batteries exhibit poor specific discharge capacity at low temperatures, and even are difficult to perform normal charging and discharging. This is mainly due to two reasons: on one hand, the ionic conductivity is reduced sharply due to the fact that the used carbonate electrolyte is solidified or partially solidified at low temperature; on the other hand, the electrochemical performance of the whole battery is rapidly reduced due to the limitation of interfacial desolvation and charge transfer at low temperature of the traditional intercalation compound single-machine material and the reduction of intrinsic ion diffusion coefficient.
The discharge capacity of the current lithium ion battery at-40 ℃ is only about 12% of the normal-temperature capacity, and obviously cannot meet the application requirements of special use environments, such as high altitude areas, aerospace, military application and other fields. Therefore, how to improve the low-temperature performance of the lithium ion battery and design and develop a high-performance low-temperature battery system is a hot direction of current research.
Disclosure of Invention
One of the objects of the present invention is: by providing the lithium ion battery, the problem that the existing lithium ion battery is poor in charge and discharge performance under a low-temperature condition is solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a lithium ion battery comprises a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate and electrolyte; the active substance of the positive plate comprises a nano nickel-based Prussian blue material; the active substance of the negative plate comprises a graphite material with the surface subjected to carbon coating treatment; the diaphragm is a polyolefin film coated with a ceramic material on the surface; the electrolyte is an electrolyte with low-temperature performance.
The battery provided by the invention takes the nano nickel-based Prussian blue material as the positive electrode, the carbon-coated graphite material as the negative electrode, and the battery core is prepared by the nano nickel-based Prussian blue material and the diaphragm coated with the ceramic material on the surface and is placed in the electrolyte with low temperature performance to perform the combined action, so that the battery still has reversible charge and discharge performance and excellent capacity retention rate at ultralow temperature of-70 ℃, and the safety performance of the battery in use is ensured.
The nano nickel-based Prussian blue material has an embedded pseudo-capacitance behavior, and the behavior can promote the desolvation process at the interface; meanwhile, the carbon-coated cathode can increase the conductivity of graphite, not only improve the transmission rate of lithium ions and provide more lithium-inserting sites, reduce the risk of charging and lithium precipitation under the low-temperature condition and reduce the irreversible capacity loss, but also improve the compatibility of the electrolyte and the cathode, reduce the probability that solvent molecules in the electrolyte with low-temperature performance are easily embedded into the graphite cathode together with the lithium ions, ensure that the inside of the battery has a faster ion diffusion coefficient by the synergistic action with the anode, and accelerate the diffusion of the ions from an interface to an intrinsic material; the adopted diaphragm can neutralize free HF in the electrolyte, so that the acid resistance of the battery is improved, and the safety performance is improved. The four components are mutually influenced and mutually promoted, so that the excellent low-temperature performance of the battery at low temperature is ensured.
Preferably, the nickel-based prussian blue material is an open framework structure. The open nano-framework structure can carry out rapid ion conduction, and the ion diffusion coefficient can reach 10 at normal temperature-9cm2S, still up to 10 at-70 ℃ at low temperature-10cm2/s。
Preferably, the graphite material is a graphite material having a large interlayer spacing and a small particle size. The graphite material with large interlayer spacing can improve the transmission rate of lithium ions, and the control of the particle size of graphite to be small particle size can reduce the transmission path of lithium ions, and the low-temperature performance of the battery is improved by matching with the effects of the anode material, the diaphragm and the electrolyte.
Preferably, the electrolyte comprises LiPF6、LiBF4、LiBOB、LiDFOB、LiFSi、LiTFSi、LiPF2O2At least two lithium salts and a solvent.
Preferably, the solvent is a mixed solvent of EC, DMC, EMC and PC, wherein the mass ratio of EC, DMC, EMC and PC is (13-20): (33-37): (35-39): (10-15). In the conventionally adopted electrolyte solvents, a composite solvent of EC and DMC is generally adopted, but the EC melting point is higher, and the EC and DMC are easy to crystallize and separate out at low temperature, so that the low-temperature performance of the lithium battery is poor. And PC can effectively inhibit the crystallization of EC at low temperature, thereby effectively improving the low-temperature performance of the battery. However, in the conventional electrolyte solvent, PC is generally rarely used as an electrolyte component, mainly because PC is easily co-inserted into the graphite negative electrode together with lithium ions, so that the graphite layer is exfoliated, thereby causing a decrease in the cycle performance of the battery. In the battery, the graphite cathode coated with carbon is adopted, so that more lithium insertion sites are provided, and the compatibility of the electrolyte and the cathode is improved; the nickel-based Prussian blue material is also adopted as the anode, and the embedded pseudo-capacitance behavior of the nickel-based Prussian blue material can promote the desolvation process at the interface, so that the PC and the lithium ions are further prevented from being embedded in the graphite cathode together; in addition, the electrolyte also adopts the composite lithium salt, certain defects of a single salt system are overcome, so that the electrolyte system with more excellent performance is obtained, the composite salt electrolyte system and a graphite material form a stable, thin and compact SEI film to protect oxygen-containing functional groups on the surface of graphite, on one hand, the electrolyte is prevented from continuously generating reduction reaction to consume limited lithium ions, on the other hand, the composite salt electrolyte system and a nickel-based Prussian blue material act together to further promote the desolvation process of solvated lithium ions, and the deintercalation of the lithium ions is ensured.
Preferably, the lithium salt is LiPF6And LiTFSi or LiPF6And LiFeSi or LiPF6And mixtures of LiDFOB. The electrolyte material selected by the battery has excellent lithium ion transmission performance under the low-temperature condition, and simultaneously avoids the situation that the components of the electrolyte and lithium ions are embedded into the graphite negative electrode together as much as possible. More preferably, a complex lithium salt LiPF is used6And the conductivity of the electrolyte of the LiTFSi can still reach 2.2ms/cm at the temperature of minus 40 ℃.
Preferably, the separator is a polyolefin film coated with aluminum oxide on the surface. The polyolefin film is preferably a PE film, and has excellent low-temperature resistance compared with a PP film, the lowest use temperature can reach-70 to-100 ℃, the melting point is lower, and the polyolefin film can be used more stably under the low-temperature condition. The aluminum oxide is used as a ceramic coating layer, and on one hand, the aluminum oxide is used as an inorganic substance, has high thermal stability and chemical inertia, and can keep the complete shape of the diaphragm at the temperature of more than 180 ℃; on the other hand, the electrolyte can neutralize free HF in the electrolyte, the acid resistance of the battery is improved, the electrolyte can still be stably used under the low-temperature condition, and the safety performance of the battery is improved on the whole.
Preferably, the particle size of the aluminum oxide is nano-scale.
The second purpose of the invention is to provide a preparation method of a lithium ion battery, which comprises the following steps:
s1, mixing the nano nickel-based Prussian blue material with a conductive agent and a positive electrode adhesive to prepare a positive electrode sheet;
s2, mixing the graphite material, the carbon coating material, the conductive agent and the negative electrode adhesive to prepare a negative electrode sheet;
s3, assembling the positive plate, the diaphragm and the negative plate into a battery cell, wherein the diaphragm is a polyolefin film with a ceramic material coated on the surface; and then injecting electrolyte with low-temperature performance to finish the preparation of the lithium ion battery.
The carbon coating material can adopt sodium carboxymethylcellulose (CMC), the CMC is used as a coating agent, and after the CMC is coated, a complete and extremely-thin amorphous carbon layer can be formed on the surface of the graphite material, so that the specific surface area and the compaction density of graphite fragments are effectively reduced, and the low-temperature performance of the battery cell is improved.
Preferably, the relative humidity of the positive plate during preparation is less than or equal to 10%; the relative humidity of the negative plate during preparation is less than or equal to 20%. The control of the relative humidity can ensure the stability of the structure of Prussian blue on one hand and is beneficial to the carbon coating of graphite on the other hand.
Compared with the prior art, the invention has the beneficial effects that: the battery provided by the invention takes the nano nickel-based Prussian blue material as the positive electrode, the carbon-coated graphite material as the negative electrode, and the battery core is prepared by the nano nickel-based Prussian blue material and the diaphragm coated with the ceramic material on the surface and is placed in the electrolyte with low temperature performance to perform the combined action, so that the battery still has reversible charge and discharge performance and excellent capacity retention rate at ultralow temperature of-70 ℃, and the safety performance of the battery in use is ensured.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantageous effects will be described in further detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a lithium ion battery comprises the following steps:
s1, mixing the nano nickel-based Prussian blue material with conductive carbon black (SP) and polyvinylidene fluoride (PVDF) according to the mass ratio of 94:3:3 at the relative humidity of less than or equal to 10% and the temperature of 25 ℃ to prepare a positive plate;
s2, mixing the graphite material, the sodium carboxymethyl cellulose (CMC), the conductive agent and the negative pole adhesive according to the mass ratio of 95:1:2:2 at the relative humidity of less than or equal to 20% at 25 ℃ to prepare a negative pole piece;
s3, taking the mass ratio of EC, DMC, EMC and PC as (13-20): (33-37): (35-39): (10-15) an electrolyte solvent is configured, the specific mixture ratio adopted in the embodiment is 16:35:37:12, and the electrolyte with low EC content and high DMC/EMC/PC solvent content is adopted, so that the low-temperature performance of the battery cell can be greatly improved; the lithium salt of the electrolyte adopts a composite lithium salt LiPF6And LiTFSi, LiPF6And the concentration of LiTFSi is 0.45 mol/L;
s4, coating a nano-scale aluminum oxide material on the surface of a PE (polyethylene) substrate to prepare a diaphragm;
and S5, assembling the positive plate, the diaphragm and the negative plate into a battery cell, and then injecting electrolyte with low-temperature performance to finish the preparation of the lithium ion battery.
Example 2
Different from example 1, the positive electrode sheet used was a nickel-based prussian blue material which was not subjected to nanocrystallization.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
Different from the embodiment 1, the positive electrode plate adopts a material, and the active material of the positive electrode plate adopts a nano manganese-based Prussian blue material in the embodiment.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is the material used for the negative electrode sheet, and in this example, the graphite material carbon-coated with pitch is used for the negative electrode sheet active material.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is the material used for the negative electrode sheet, and in this example, the active material of the negative electrode sheet is made of a common graphite material and is not coated with carbon.
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
The difference from the embodiment 1 is the material used for the diaphragm, in this embodiment, the diaphragm is a PE film, and the surface of the PE film is coated with a silica material.
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
The difference from the embodiment 1 is the material used for the diaphragm, in this embodiment, the diaphragm is a PE film, and the surface of the PE film is coated with a magnesium oxide material.
The rest is the same as embodiment 1, and the description is omitted here.
Example 8
The difference from the embodiment 1 is the material used for the diaphragm, in this embodiment, the diaphragm is a common PE film, and the surface of the diaphragm is not coated with a ceramic material.
The rest is the same as embodiment 1, and the description is omitted here.
Example 9
The difference from the example 1 is the composition of the electrolyte, in this example, EC, DMC, EMC are used as solvent, LiPF6An electrolyte is provided for the lithium salt.
The rest is the same as embodiment 1, and the description is omitted here.
Example 10
The difference from the example 1 is the composition of the electrolyte, in this example, EC, DMC, EMC are used as solvent, LiPF6And LiTFSi as the lithium salt.
The rest is the same as embodiment 1, and the description is omitted here.
Example 11
The difference from example 1 is the composition of the electrolyte, in this example LiPF is used as the electrolyte6And LiFeSi as a composite lithium salt to prepare an electrolyte.
The rest is the same as embodiment 1, and the description is omitted here.
Example 12
Different from the embodiment 1 in the materials adopted by the positive plate and the negative plate, the active substance of the positive plate in the embodiment comprises nickel-based Prussian blue material which is not subjected to nanocrystallization; the active substance of the negative plate is a graphite material coated with carbon by adopting asphalt.
The rest is the same as embodiment 1, and the description is omitted here.
Example 13
Different from the embodiment 1, the negative electrode sheet and the diaphragm are made of materials, and the active substance of the negative electrode sheet in the embodiment is made of graphite material which is carbon-coated by asphalt; the diaphragm is a PE film coated with a magnesium oxide material on the surface.
The rest is the same as embodiment 1, and the description is omitted here.
Example 14
Different from the embodiment 1 in the composition of the material and the electrolyte adopted by the negative electrode plate, the active material of the negative electrode plate in the embodiment adopts a graphite material which is carbon-coated by asphalt; the electrolyte is LiPF6Is prepared for lithium salt.
The rest is the same as embodiment 1, and the description is omitted here.
Example 15
Different from the embodiment 1, the negative electrode sheet and the diaphragm adopt materials and the composition of electrolyte, and the active substance of the negative electrode sheet in the embodiment adopts graphite material which is carbon-coated by asphalt; the diaphragm is a PE film coated with magnesium oxide material on the surface, and the electrolyte is LiPF6Is prepared for lithium salt.
The rest is the same as embodiment 1, and the description is omitted here.
Example 16
Different from the embodiment 1, the negative electrode sheet and the diaphragm adopt materials and the composition of electrolyte, and the active substance of the negative electrode sheet in the embodiment adopts graphite material which is carbon-coated by asphalt; the diaphragm is a PE film coated with magnesium oxide material on the surface, and the electrolyte is LiPF6And LiFeSi as lithium salt.
The rest is the same as embodiment 1, and the description is omitted here.
The batteries prepared in examples 1 to 16 were subjected to performance tests, and the test results are shown in table 1.
TABLE 1
Figure BDA0002710618870000071
Figure BDA0002710618870000081
It can be seen from examples 1 to 3 that the nickel-based prussian blue nano-material used as the positive electrode has more excellent performance, mainly because the nickel-based prussian blue material has an embedded pseudocapacitance behavior which can promote the desolvation process at the interface, so that lithium ions can be more freely embedded and extracted, and the ion diffusion coefficient can still reach 10 at a low temperature of-70 DEG C-10cm2And s. Examples 1, 4 to 5 show that the carbon-coated negative electrode material has more excellent performance at low temperature than the conventional graphite negative electrode material. This is mainly because carbon coating can increase the conductivity of graphite, can increase the transport rate of lithium ions and provide more lithium intercalation sites. The CMC is adopted as the carbon coating material of the cathode, compared with other substances such as asphalt and the like as the carbon coating material, the CMC is more excellent in improving the low-temperature performance of the battery, so that an amorphous carbon layer formed on the surface of a graphite material is thinner and more complete after the CMC is coated, and the specific surface area and the compaction density of graphite fragments are greatly reduced; by comparison with example 12, it is clear that the CMC-coated stoneThe synergistic effect of the ink material and the nickel-based Prussian blue material is stronger, and the diffusion of lithium ions from the interface to the intrinsic material is further accelerated.
In addition, as is clear from examples 1 and 6 to 8, the separators using the surface coating material layer are also superior in low-temperature performance to conventional separators. This is mainly because the surface coating on the one hand neutralizes free HF in the electrolyte; on one hand, the stability of the polyolefin film can be ensured, and the complete shape and the working performance of the polyolefin film can still be ensured under the low-temperature condition. The aluminum oxide is adopted as the coating layer, compared with other ceramic layers, the low-temperature performance of the battery is more favorably improved, on one hand, the aluminum oxide has excellent performance, and on the other hand, a certain synergistic effect exists between the diaphragm of the material and the anode, the cathode and the electrolyte, so that the PE film coated with the aluminum oxide can be more matched with the battery for use under the low-temperature condition, and the specific materials adopted by the anode, the cathode, the diaphragm and the electrolyte are different from one another and have greater influence on the use of the PE film under the low-temperature condition by embodiments 13-16; among them, the performance of the battery prepared by using the material in example 1 at a low temperature of-70 ℃ is the best. In addition, as can be seen from examples 1 and 9 to 11, the low-content EC, the high-content DMC/EMC/PC and the composite lithium salt adopted by the invention act together, and the lithium ion transport performance is more excellent under the low-temperature condition.
According to the test results, the excellent performance at low temperature is benefited by the mutual matching effect of the positive electrode, the negative electrode, the diaphragm and the electrolyte, and the battery can still be reversibly charged and discharged at-70 ℃ through the synergistic effect, so that the battery has excellent capacity retention rate.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (10)

1. A lithium ion battery is characterized by comprising a positive plate, a negative plate, a diaphragm arranged between the positive plate and the negative plate and electrolyte; the active substance of the positive plate comprises a nano nickel-based Prussian blue material; the active substance of the negative plate comprises a graphite material with the surface subjected to carbon coating treatment; the diaphragm is a polyolefin film coated with a ceramic material on the surface; the electrolyte is an electrolyte with low-temperature performance.
2. The lithium ion battery of claim 1, wherein the nickel-based Prussian blue material is an open framework structure.
3. The lithium ion battery of claim 1, wherein the graphite material is a graphite material having a large interlamellar spacing and a small particle size.
4. The lithium ion battery of claim 1, wherein the electrolyte comprises LiPF6、LiBF4、LiBOB、LiDFOB、LiFSi、LiTFSi、LiPF2O2At least two lithium salts and a solvent.
5. The lithium ion battery of claim 4, wherein the solvent is a mixed solvent of EC, DMC, EMC and PC, and the mass ratio of EC, DMC, EMC and PC is (13-20): (33-37): (35-39): (10-15).
6. The lithium ion battery of claim 5, wherein the lithium salt is LiPF6And LiTFSi or LiPF6And LiFeSi or LiPF6And mixtures of LiDFOB.
7. The lithium ion battery according to any one of claims 1 to 6, wherein the separator is a polyolefin film coated with aluminum oxide on the surface.
8. The lithium ion battery according to claim 7, wherein the particle size of the alumina is on the nanometer scale.
9. A preparation method of a lithium ion battery is characterized by comprising the following steps:
s1, mixing the nano nickel-based Prussian blue material with a conductive agent and a positive electrode adhesive to prepare a positive electrode sheet;
s2, mixing the graphite material, the carbon coating material, the conductive agent and the negative electrode adhesive to prepare a negative electrode sheet;
s3, assembling the positive plate, the diaphragm and the negative plate into a battery cell, wherein the diaphragm is a polyolefin film with a ceramic material coated on the surface; and then injecting electrolyte with low-temperature performance to finish the preparation of the lithium ion battery.
10. The method for preparing a lithium ion battery according to claim 9, wherein the relative humidity of the positive electrode sheet during preparation is less than or equal to 10%; the relative humidity of the negative plate during preparation is less than or equal to 20%.
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