CN109449494B - Preparation method of solid electrolyte interface layer of lithium ion battery and lithium ion battery - Google Patents
Preparation method of solid electrolyte interface layer of lithium ion battery and lithium ion battery Download PDFInfo
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- CN109449494B CN109449494B CN201811314692.1A CN201811314692A CN109449494B CN 109449494 B CN109449494 B CN 109449494B CN 201811314692 A CN201811314692 A CN 201811314692A CN 109449494 B CN109449494 B CN 109449494B
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
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- H—ELECTRICITY
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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 preparation method of a solid electrolyte interface layer of a lithium ion battery and the lithium ion battery, and relates to the technical field of battery preparation. The preparation method of the solid electrolyte interface layer of the lithium ion battery adopts a continuous ion layer adsorption reaction method, and a compact solid electrolyte interface layer is deposited on the surface of a negative pole piece, wherein the solid electrolyte interface layer mainly comprises LiPON (Passive optical network) which is used for H (hydrogen peroxide) reaction 2 O、O 2 And the electrolyte has stable properties, so that side reactions are avoided, the reaction of the electrolyte with the negative pole piece and the solid electrolyte interface layer is prevented, and the capacity, the rate capability and the thermal stability of the battery are effectively improved. According to the lithium ion battery provided by the invention, the compact solid electrolyte interface layer is formed on the surface of the negative pole piece by adopting the method, so that the lithium ion battery has higher multiplying power performance, meanwhile, the potential safety hazard caused by lithium dendrites is reduced, and the safety performance is higher.
Description
Technical Field
The invention relates to the technical field of battery preparation, in particular to a preparation method of a solid electrolyte interface layer of a lithium ion battery and the lithium ion battery.
Background
Lithium ion batteries are widely used due to their ultra-high energy density, but lithium ions are prone to form lithium dendrites during repeated intercalation, which not only affect battery capacity, but more importantly can cause potential safety hazards. Therefore, the prevention of the formation of lithium dendrites is one of the important problems to be solved urgently in the application process of lithium ion batteries.
At present, in order to effectively prevent the formation of lithium dendrite, a mode of coating a solid electrolyte film on a positive electrode and a negative electrode of a lithium ion battery is mostly adopted, but due to the precision problem of coating equipment, the coating layer cannot be guaranteed to be a uniform and compact solid electrolyte film.
In view of this, designing and manufacturing a method for preparing a solid electrolyte interface layer of a lithium ion battery, which can prevent the formation of lithium dendrites, improve the capacity and the cycle life of the lithium ion battery, is a technical problem that needs to be improved urgently in the technical field of battery preparation at present.
Disclosure of Invention
The invention aims to provide a preparation method of a solid electrolyte interface layer of a lithium ion battery, which can avoid the loss of battery capacity caused by SEI film synthesis by adopting a continuous ion layer adsorption reaction method to form a compact solid electrolyte layer on the surface of a negative pole piece, thereby improving the energy density of materials and the rate capability of the battery.
The invention also aims to provide a lithium ion battery which comprises a negative pole piece, a solid electrolyte interface layer, a positive pole piece and electrolyte. The solid electrolyte interface layer is prepared by the preparation method of the solid electrolyte interface layer of the lithium ion battery and is deposited on the surface of the negative pole piece, so that the formation of lithium dendrites can be effectively prevented, and the capacity, the rate capability, the thermal stability and the safety performance of the battery can be effectively improved.
The technical problem of the invention is solved by adopting the following technical scheme.
The invention provides a preparation method of a solid electrolyte interface layer of a lithium ion battery, which is characterized in that a solid electrolyte layer is formed on the surface of a negative pole piece by adopting a continuous ionic layer adsorption reaction method, and the preparation method comprises the following steps:
step 1, placing a negative pole piece in a nitrogen atmosphere under a preset temperature condition;
step 2, putting the negative pole piece into a lithium hydroxide solution for surface adsorption;
step 3, placing the negative pole piece adsorbed in the step 2 in the nitrogen atmosphere again;
step 4, putting the negative pole piece obtained in the step 3 into H 3 PO 4 Surface adsorption is carried out in the solution.
Further, the step 1 to the step 4 are circulated, and the circulation times are 5 to 30 times.
Further, in the step 1, the nitrogen gas is high-purity nitrogen gas.
Further, in the step 1, the preset temperature is-50 ℃ to-30 ℃.
Further, in the step 1, the time period of placing the negative electrode plate in the nitrogen atmosphere is 5 to 60 minutes.
Further, in the step 2, the lithium hydroxide solution is a saturated solution.
Further, in the step 3, the nitrogen atmosphere is high-purity nitrogen, and the temperature is-45 ℃ to-35 ℃.
Further, in the step 4, the H 3 PO 4 The solution was saturated.
The invention provides a lithium ion battery which comprises a negative pole piece, a solid electrolyte interface layer, a positive pole piece and electrolyte. The solid electrolyte interface layer is prepared by the preparation method of the solid electrolyte interface layer of the lithium ion battery and is deposited on the negative electrode plate.
The lithium ion battery is prepared by rolling, winding, baking, injecting, aging and forming the negative pole piece, the solid electrolyte interface layer, the positive pole piece and the electrolyte.
Further, the positive pole piece is made of any one of lithium iron phosphate, lithium cobaltate or lithium manganate. The negative pole piece is made of any one of metal lithium, artificial or natural graphite or Si-C.
The preparation method of the solid electrolyte interface layer of the lithium ion battery and the lithium ion battery provided by the invention have the following beneficial effects:
the preparation method of the solid electrolyte interface layer of the lithium ion battery provided by the invention is simple and convenient to operate. A compact solid electrolyte interface layer is formed on the surface of the negative electrode by adopting a continuous ion-exchange membrane adsorption reaction method (SILAR), so that the loss of battery capacity caused by the synthesis of an SEI film can be avoided, and the energy density of the material is further improved. The solid electrolyte interface layer mainly comprises LiPON, so that the solid electrolyte interface layer has excellent electronic insulation and ion conductivity, and the rate capability of the battery can be greatly improved. And this solid electrolyte boundary layer has certain mechanical strength, covers on negative pole piece surface, can prevent that lithium dendrite from impaling the potential safety hazards such as barrier film causes short circuit explosion, can completely cut off the contact of negative pole piece and electrolyte simultaneously, has prevented the decomposition reaction of electrolyte with the negative pole piece, has avoided because the capacity loss that the reaction of the two caused. The preparation method of the solid electrolyte interface layer of the lithium ion battery has simple process, has obvious effect on improving the performance of the lithium ion battery, and has great popularization and application values.
The lithium ion battery provided by the invention comprises a negative pole piece, a solid electrolyte interface layer, a positive pole piece and electrolyte. The solid electrolyte interface layer is prepared by the preparation method of the solid electrolyte interface layer of the lithium ion battery and is deposited on the negative pole piece. The lithium ion battery is prepared by rolling, winding, baking, injecting, aging and forming the negative pole piece, the solid electrolyte interface layer, the positive pole piece and the electrolyte. The lithium ion battery has the advantages that the compact solid electrolyte interface layer is formed on the surface of the negative pole piece, so that the loss of battery capacity caused by the synthesis of an SEI (solid electrolyte interphase) film can be avoided, and the energy density of the material is further improved. Meanwhile, the compact solid electrolyte interface layer has certain mechanical strength, covers the surface of the negative pole piece, can prevent potential safety hazards such as short circuit explosion caused by the fact that the lithium dendrite pierces the isolating membrane, and is high in safety performance.
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 a schematic process flow diagram of a method for preparing a solid electrolyte interface layer of a lithium ion battery according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "upper", "lower", and the like refer to orientations or positional relationships based on orientations or positional relationships shown in the drawings, or orientations or positional relationships conventionally used in the use of products of the present invention, or orientations or positional relationships routinely understood by those skilled in the art, which are merely for convenience of description and simplification of the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore, should not be construed as limiting the present invention.
The terms "first", "second", etc. in the description of the present invention are used for distinguishing between them and not for distinguishing between them.
In the description of the present invention, it should also be noted that, unless otherwise explicitly stated or limited, the terms "disposed" and "mounted" are to be construed broadly, e.g., as being fixedly attached, detachably attached, or integrally attached; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Formation, i.e., a process in which an Electrolyte and an Electrolyte react on a battery negative electrode to form a Solid Electrolyte Interface (SEI) film, is an important process in the production process of a lithium ion battery. The SEI film is an electronic insulator but an excellent conductor of lithium ions, and the uniform and stable SEI film can stably exist in the organic electrolyte well and can prevent solvent molecules from directly contacting with an electrode material, so that damage to the electrode material caused by co-intercalation of the solvent molecules is avoided, and the formed uniform and stable SEI film plays a vital role in various electrochemical performances of the lithium ion battery, such as circulation, multiplying power, storage, safety performance and the like.
However, in the conventional formation process, the SEI film consumes part of lithium ions, so that the initial charge-discharge irreversible capacity is increased, the initial charge-discharge efficiency of the electrode material is reduced, the utilization rate of the positive electrode material and the negative electrode material is low, and the manufacturing cost of the battery is correspondingly increased. Meanwhile, in the use process of the battery, the electrolyte can react with the anode material and the cathode material to consume the electrolyte and the anode material and the cathode material, so that the capacity and the cycle life of the battery are reduced, and gas can be generated to expand the battery, thereby influencing the electrochemical performance and the safety performance. In addition, lithium dendrites are generated in the process of charging and discharging or abuse of the lithium ion battery, and the lithium dendrites can pierce through the isolating membrane along with the continuous growth of the lithium dendrites, so that potential safety hazards such as short circuit explosion are caused.
In order to overcome the defects, according to the preparation method of the solid electrolyte interface layer of the lithium ion battery, a compact solid electrolyte interface layer, namely an SEI (solid electrolyte interface layer), is formed on the surface of a negative electrode by adopting a continuous ionic layer adsorption reaction method (SILAR), so that the loss of battery capacity caused by the synthesis of the SEI can be avoided, and the energy density of the material is improved. The SEI film mainly comprises LiPON, so that the SEI film has excellent electronic insulation and ion conductivity, and the rate performance of the battery can be greatly improved. Moreover, the solid electrolyte SEI film has certain mechanical strength, covers the surface of the negative electrode, can prevent potential safety hazards such as short circuit explosion and the like caused by the fact that the lithium dendrite pierces the isolating film, can isolate the contact between the negative electrode and the electrolyte, prevents the decomposition reaction between the electrolyte and the negative electrode, and avoids capacity loss caused by the reaction between the negative electrode and the electrolyte.
Fig. 1 is a schematic process flow diagram of a method for preparing a solid electrolyte interface layer of a lithium ion battery according to an embodiment of the present invention, and fig. 1 is shown.
The preparation method of the solid electrolyte interface layer of the lithium ion battery provided by the embodiment comprises the following specific steps:
s1, placing a negative pole piece in a nitrogen atmosphere under a preset temperature condition;
s2, putting the negative pole piece into a lithium hydroxide solution for surface adsorption;
s3, placing the negative pole piece adsorbed in the step 2 in a nitrogen atmosphere again;
s4, putting the negative pole piece obtained in the step 3 into H 3 PO 4 Surface adsorption is carried out in the solution.
And (5) circularly executing the step (1) to the step (4), wherein the circulating times are 5 to 30. Preferably, the number of cycles may also be 10 to 20.
In the step 1, the preset temperature is-50 ℃ to-30 ℃, preferably, in this embodiment, the preset temperature is controlled at a dew point of-40 ℃, and the nitrogen atmosphere adopts high-purity nitrogen, that is, nitrogen with a purity of more than 99.999%. The time of the step 1 operation may be 5 minutes to 60 minutes, such as 10 minutes, 20 minutes, 30 minutes, etc., depending on the actual situation, and is not particularly limited herein.
In the step 2, the lithium hydroxide solution is a saturated solution, and the negative electrode plate obtained in the step 1 is immersed in the lithium hydroxide saturated solution for a period of time, for example, 5 to 20 minutes, to perform surface adsorption.
In the step 3, after the step 2 is executed, the negative pole piece is placed in a high-purity nitrogen atmosphere, the temperature is controlled to be between minus 45 ℃ and minus 35 ℃, and preferably, the temperature is controlled to be minus 40 ℃. The operating time of step 3 is 5 to 60 minutes.
In step 4, putting the negative pole piece obtained in the step 3 into H 3 PO 4 In the solution, surface adsorption was performed. Preferably, H 3 PO 4 The solution is saturated solution, and the operation time of the step 4 is 5 minutes to 60 minutes. And (5) circularly operating the steps 1 to 4 to enable the surface of the negative pole piece to continuously adsorb and deposit an SEI film.
It is easy to understand that, in the process of performing steps 1 to 4 cyclically, the following chemical reactions occur on the surface of the negative pole piece:
formula 1:3LiOH + H 3 PO 4 ＝Li 3 PO 4 +3H 2 O，
Formula 2:
since LiOH and H are adsorbed on the surface of the negative pole piece in the step 2 and the step 4 respectively 3 PO 4 That is, the chemical reaction of formula 1 occurs on the surface of the negative electrode plate to generate Li 3 PO 4 . Then, the negative pole piece is placed in a high-purity nitrogen atmosphere, namely, the chemical reaction shown in the formula 2 can occur on the surface of the negative pole piece, the LIPON is formed on the surface of the negative pole piece, and the two chemical reactions continuously occur through the cyclic operation steps 1 to 4, so that the adsorption and deposition are continuously carried out on the surface of the negative pole piece to form a compact SEI film, wherein the main component of the SEI film is LIPON, and the LIPON is used for H 2 O、O 2 And the electrolyte has stable properties, so that side reactions are avoided, the reaction of the electrolyte with the negative pole piece and the solid electrolyte interface layer is prevented, and the capacity, the rate capability and the thermal stability of the battery are effectively improved.
The lithium ion battery provided by the invention comprises a negative pole piece, a solid electrolyte interface layer, a positive pole piece and electrolyte. The solid electrolyte interface layer is prepared by the preparation method of the solid electrolyte interface layer of the lithium ion battery and is deposited on the negative electrode plate. The lithium ion battery is prepared by rolling, winding, baking, injecting, aging and forming the negative pole piece, the solid electrolyte interface layer, the positive pole piece and the electrolyte. The positive pole piece is made of any one of lithium iron phosphate, lithium cobaltate or lithium manganate. The negative pole piece is made of any one of metal lithium, artificial or natural graphite or Si-C.
In the lithium ion battery provided in this embodiment, a solid electrolyte LiPON is deposited on the surface of a negative electrode plate, taking a ternary positive electrode and graphite negative electrode system as an example, the positive electrode material may also be lithium iron phosphate, lithium cobaltate, lithium manganate, and the like, and the negative electrode material may be metallic lithium, artificial or natural graphite, a Si — C negative electrode, and the like. The lithium ion battery has the advantages that the compact solid electrolyte interface layer is formed on the surface of the negative pole piece, so that the loss of battery capacity caused by the synthesis of an SEI (solid electrolyte interphase) film can be avoided, and the energy density of the material is improved. Meanwhile, the compact solid electrolyte interface layer has certain mechanical strength, covers the surface of the negative pole piece, can prevent potential safety hazards such as short circuit explosion and the like caused by the fact that the lithium dendrite pierces the isolating membrane, and is high in safety performance.
In order to verify the effect of the preparation method of the solid electrolyte interface layer of the lithium ion battery on improving the performance of the lithium ion battery, the following comparative tests were carried out. Example 1 is a lithium ion battery manufactured by the method for manufacturing a solid electrolyte interface layer of a lithium ion battery provided in this example, and example 2 is a comparative experiment.
Example 1
The positive pole of the lithium ion battery comprises NCM, super-P and PVDF, the negative pole comprises artificial graphite, super-P, SBR and CMC, pole pieces are respectively prepared by batching and coating, a layer of solid electrolyte LiPON is deposited on the surface of the negative pole piece by a continuous ion layer adsorption reaction method, the steps 1 to 4 are circulated for 10 times, and then rolling, winding, baking, liquid injection, aging and formation are carried out.
Example 2
The positive pole of the lithium ion battery comprises NCM, super-P and PVDF, the negative pole comprises artificial graphite, super-P, SBR and CMC, and the pole pieces are prepared by batching and coating respectively, and then rolling, winding, baking, injecting liquid, aging and forming are carried out.
In example 2, except that LiPON is not deposited on the surface of the negative electrode plate, the other manufacturing methods and manufacturing conditions are the same as those in example 1, the electrochemical performance comparison results of the two are shown in table 1, and table 1 is the battery capacity, 3C rate performance and cycle performance test results of example 1 and example 2.
Table 1:
as can be seen from table 1, the battery capacity, rate discharge performance and cycle performance of example 1 are significantly better than those of example 2, and the performance advantages are derived from the electronic insulation, ion conductivity and chemical stability of LiPON on the surface of the negative electrode plate, so that the material can be isolated to prevent side reactions and improve the conductivity.
In summary, the preparation method of the solid electrolyte interface layer of the lithium ion battery and the lithium ion battery provided by the invention have the following beneficial effects:
according to the preparation method of the solid electrolyte interface layer of the lithium ion battery, a compact solid electrolyte interface layer is formed on the surface of the negative electrode by adopting a continuous ionic layer adsorption reaction method (SILAR), so that the loss of battery capacity caused by the synthesis of an SEI film can be avoided, and the energy density of the material is further improved. The solid electrolyte interface layer mainly comprises LiPON, so that the solid electrolyte interface layer has excellent electronic insulation and ion conductivity, and the rate capability of the battery can be greatly improved. And this solid electrolyte interface layer has certain mechanical strength, covers on the negative pole piece surface, can prevent that lithium dendrite from impaling the potential safety hazards such as short circuit explosion that causes the barrier film, can completely cut off the contact of negative pole piece and electrolyte simultaneously, has prevented the decomposition reaction of electrolyte and negative pole piece, has avoided because the capacity loss that the reaction of the two caused. The preparation method of the solid electrolyte interface layer of the lithium ion battery has simple process, has obvious effect on improving the performance of the lithium ion battery, and has great popularization and application value.
The lithium ion battery provided by the invention comprises a negative pole piece, a solid electrolyte interface layer, a positive pole piece and electrolyte. The solid electrolyte interface layer is prepared by the preparation method of the solid electrolyte interface layer of the lithium ion battery and is deposited on the negative electrode plate. The lithium ion battery is prepared by rolling, winding, baking, injecting liquid, aging and forming the negative pole piece, the solid electrolyte interface layer, the positive pole piece and the electrolyte. The lithium ion battery has the advantages that the compact solid electrolyte interface layer is formed on the surface of the negative pole piece, so that the loss of battery capacity caused by the synthesis of an SEI (solid electrolyte interphase) film can be avoided, and the energy density of the material is further improved. Meanwhile, the compact solid electrolyte interface layer has certain mechanical strength, covers the surface of the negative pole piece, can prevent potential safety hazards such as short circuit explosion caused by the fact that the lithium dendrite pierces the isolating membrane, and is high in safety performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, as it will be apparent to those skilled in the art that various modifications, combinations and variations can be made in the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a solid electrolyte interface layer of a lithium ion battery is characterized in that a solid electrolyte layer is formed on the surface of a negative pole piece by adopting a continuous ionic layer adsorption reaction method, and the preparation method comprises the following steps:
step 1, placing a negative pole piece in a nitrogen atmosphere under a preset temperature condition; wherein the preset temperature is-50 ℃ to-30 ℃;
step 2, putting the negative pole piece into a lithium hydroxide solution for surface adsorption;
step 3, placing the negative pole piece adsorbed in the step 2 in the nitrogen atmosphere again, and controlling the temperature to be between-45 ℃ and-35 ℃;
step 4, putting the negative pole piece obtained in the step 3 into H 3 PO 4 Carrying out surface adsorption in the solution; wherein the negative pole piece adopts artificial or natural graphite or Si-CAny one of the above.
2. The method of preparing a solid electrolyte interface layer of a lithium ion battery according to claim 1, wherein the step 1 to the step 4 are cycled for 5 to 30 times.
3. The method for preparing a solid electrolyte interface layer of a lithium ion battery according to claim 1, wherein the nitrogen gas in the step 1 is a high purity nitrogen gas.
4. The method for preparing a solid electrolyte interface layer of a lithium ion battery according to claim 1, wherein the predetermined temperature in step 1 is-50 ℃ to-40 ℃.
5. The method for preparing the solid electrolyte interface layer of the lithium ion battery according to claim 1, wherein in the step 1, the negative electrode plate is placed in the nitrogen atmosphere for a period of time ranging from 5 minutes to 60 minutes.
6. The method for preparing a solid electrolyte interface layer of a lithium ion battery according to claim 1, wherein in the step 2, the lithium hydroxide solution is a saturated solution.
7. The method for preparing a solid electrolyte interface layer of a lithium ion battery according to claim 1, wherein the nitrogen atmosphere in step 3 is high purity nitrogen and the temperature is from-45 ℃ to-40 ℃.
8. The method of claim 1, wherein in step 4, the H is the interface layer of the lithium ion battery solid electrolyte 3 PO 4 The solution was saturated.
9. A lithium ion battery is characterized by comprising a negative pole piece, a solid electrolyte interface layer, a positive pole piece and electrolyte; the solid electrolyte interface layer is prepared by the preparation method of the lithium ion battery solid electrolyte interface layer of any one of claims 1 to 8 and is deposited on the negative electrode plate;
the lithium ion battery is prepared by rolling, winding, baking, injecting, aging and forming the negative pole piece, the solid electrolyte interface layer, the positive pole piece and the electrolyte.
10. The lithium ion battery of claim 9, wherein the positive electrode sheet is made of any one of lithium iron phosphate, lithium cobaltate or lithium manganate; the negative pole piece is made of any one of artificial or natural graphite or Si-C.
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