CN106784822B - High-voltage lithium ion battery with high volume energy density - Google Patents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
Abstract
The invention provides a high-voltage lithium ion battery with high volume energy density, and belongs to the technical field of lithium ion batteries. The lithium ion battery comprises a positive plate and a negative plate, wherein the positive plate comprises a positive material and a positive binder, the negative plate comprises a negative material, and the positive material comprises lithium manganese iron phosphate; the positive electrode binder is PVDF; the cathode material is a nano carbon sheet/graphitized mesocarbon microbead composite material. The invention adopts LiFe1‑xMnxPO4The PVDF with low molecular weight is used as a positive electrode binder to reduce the rebound rate of the thickness of a positive electrode plate as a high-voltage positive electrode material, and meanwhile, the nano carbon plate/graphitized intermediate phase carbon microsphere composite material is used as a negative electrode material, so that the use of the negative electrode material is less by utilizing the high specific capacity, the thicknesses of the negative electrode plate and a battery are reduced, and the volume energy density of the battery is greatly improved; and the conductive film is added on the aluminum foil of the positive plate, so that the internal resistance of the battery can be effectively reduced.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-voltage lithium ion battery with high volume energy density.
[ background of the invention ]
With the continuous development of electronic products, lithium ion batteries are widely used, and the current electronic products are continuously updated and upgraded, and the requirements on lithium ion battery products are higher and higher. At present, in the whole battery industry, the product quality of each battery manufacturer is different, 90% of manufacturers are in a middle-low end horizontal state, and the battery performance can not meet the requirements on some high-requirement electronic products, such as: in the early days, the Bluetooth is mainly used, the performance requirement on the battery is not very high, enterprises with certain funds can be put into the lithium ion battery industry, and from the current market, the main electronic products are digital, tablet computers and ultrathin mobile phones, the electronic products are all touch screen displays, and the products are limited by the volume, so that the volume ratio of the lithium ion battery is required to be much higher than that of the conventional lithium ion battery, for example, the required capacity of a three-star part type mobile phone is about 12% higher than that of the conventional mobile phone under the same volume, and the requirement is difficult to achieve by the technical level of each manufacturer at present, so the polymer lithium ion battery with higher capacity becomes the first choice of the digital communication products.
With the coming of the 3G/4G era, most of the current communication products have multiple functions of surfing the internet, playing games, watching electronic books, MP3, MP4 and the like, so that the capacity requirement of the lithium ion battery is higher and higher. The common polymer lithium ion battery is influenced by the material characteristics, and the capacity of the common polymer lithium ion battery cannot meet the requirements of some special people, so a high-capacity digital communication polymer lithium ion battery has to be developed.
The gram capacity of the anode of the lithium ion battery used in the market is only 142 mAmph/gram, the requirements are difficult to meet for the large screen of the current smart phone and tablet personal computer, and the development of science and technology requires that the lithium ion battery with higher volume ratio must be provided. Higher demands are made on the performance of lithium ion batteries, in particular on the energy density and power density. The energy density of the battery is related to the specific capacity and operating voltage of the battery, and thus high voltage and large capacity are soughtThe lithium ion battery anode material has very important significance. Currently used lithium ion battery positive electrode materials, such as LiCoO2、LiMn2O4、LiFePO4、LiNixCoyMn1-x-yO2The operating voltage of the battery is lower than 4V, and the energy density and the power density of the battery are limited in application.
Therefore, 4.5V high-voltage anode material LiFe1-xMnxPO4The occurrence of (2) is of great significance. The high voltage can not only improve the energy density and the power density, but also improve the performance of the single batteries, thereby reducing the number of the single batteries which need to be connected in series and bringing advantages to the performance safety and the cost of the batteries.
[ summary of the invention ]
The invention aims to: in order to solve the above problems, an object of the present invention is to provide a high voltage lithium ion battery with high volumetric energy density, which not only uses the high voltage positive electrode material LiFe1-xMnxPO4The capacity of the battery is improved, and the capacity of the battery is improved in the aspects of battery technology and other materials, so that the volume energy density of the lithium ion battery is comprehensively improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention relates to a high-voltage lithium ion battery with high volume energy density, which comprises a positive plate and a negative plate, wherein the positive plate comprises a positive material and a positive binder, the negative plate comprises a negative material, the positive material comprises lithium manganese iron phosphate, and the iron-manganese ratio of the lithium manganese iron phosphate is 0.1-0.35: 0.65-0.90; the positive binder is PVDF, and the molecular weight of the positive binder is 30-70 ten thousand; the negative electrode material is a nano carbon sheet/graphitized mesocarbon carbon microsphere composite material, and the nano carbon sheet is a three-dimensional graphene-like nanosheet. The discharging platform of the lithium manganese iron phosphate is about 3.9V, the gram capacity of the lithium manganese iron phosphate under the multiplying power of 1.0C is more than 144mAh/g, the lithium manganese iron phosphate has more advantages in electrical property compared with the lithium iron phosphate, the iron-manganese content ratio of the lithium manganese iron phosphate is controlled, the influence of too high Fe content on the platform voltage of the battery is large, the Fe content is too low, the conductivity of the material is too low, and the capacity exertion is influenced. The molecular weight of PVDF (polyvinylidene fluoride) used in the current market of the positive electrode binder is more than 70 ten thousand, a positive electrode material is coated into a positive electrode plate and then is rolled, after the PVDF is cured, the rebound of the thickness of the electrode plate is large, and the larger the molecular weight of the PVDF is, the larger the rebound value after the rolling of the thickness of the electrode plate and after the charging and discharging is, the larger the thickness of the battery is, the further the whole volume is increased, and the reduction of the volume energy density is caused; and the PVDF with low molecular weight can effectively reduce the rebound of the positive plate after rolling and can also reduce the thickness rebound of the positive plate after charging and discharging of the battery, thereby reducing the thickness of the battery and improving the volume energy density of the battery.
The positive plate also comprises an aluminum foil, and a conductive film is arranged between the positive material and the aluminum foil, wherein the thickness of the conductive film is 1-3 mu m.
The preparation method of the nano carbon sheet/graphitized mesocarbon microbead composite material comprises the following steps:
(1) adding 200mL of 98% concentrated sulfuric acid into a 1000mL clean round-bottom flask, controlling the reaction temperature of the flask to be 2-8 ℃, adding 8g of graphitized mesocarbon microbeads through mechanical stirring, slowly adding 1.0-4.0 g of sodium nitrate for multiple times, finally slowly adding potassium permanganate for multiple times, and reacting for 2-5 hours;
(2) raising the reaction temperature to 30-40 ℃, continuously stirring for 1-5H, adding 400mL of deionized water at 60-100 ℃ under the stirring condition, raising the heating temperature to 85-105 ℃, and adding 150mL of H with the mass fraction of 10%2O2Continuously stirring for 3-7 h, and finishing the reaction;
(3) washing once by using an HCl solution with the mass fraction of 10%, washing to be neutral by using deionized water, performing vacuum filtration, and drying in an oven at 80-100 ℃ to obtain a graphitized mesocarbon microbead intermediate;
(4) and (3) reducing the graphitized intermediate phase carbon microsphere intermediate at 800-1100 ℃ under an anaerobic condition at high temperature to finally obtain the nano carbon sheet/graphitized intermediate phase carbon microsphere composite material.
The negative electrode material of the invention uses the nano carbon sheet/graphitized intermediate phase carbon microsphere composite material, wherein the capacity exertion of the graphitized intermediate phase carbon microsphere is generally 360mAh/g, after the treatment by the method of the invention, the graphene-like structural components are added between the graphitized intermediate phase carbon microspheres, the capacity exertion of the negative electrode material is greatly improved, and along with the weight ratio change of potassium permanganate and the graphitized intermediate phase carbon microsphere, the maximum capacity exertion of the obtained nano carbon sheet/graphitized intermediate phase carbon microsphere composite material can reach more than 2000, which is more than 5 times higher than that of the graphitized intermediate phase carbon microsphere, therefore, the lithium ion battery with the same capacity is produced, the using amount of the nano carbon sheet/graphitized intermediate phase carbon microsphere composite material is less, the occupation ratio of the negative electrode sheet in the battery volume is greatly reduced, and the battery volume is greatly reduced, the volumetric energy density of the battery is improved.
Before coating a positive electrode material, the positive electrode plate is firstly adhered with a layer of conductive film, wherein the conductive film can be composed of graphene and PVDF according to the weight ratio of 95-98: 2-5, and is sprayed on the aluminum foil by static electricity; or may be formed of graphene, and the conductive film is attached to the aluminum foil using a vapor deposition method. Because the graphene has very strong conductive capability, the graphene is used as a conductive film, so that the conductivity of the positive plate can be increased, the internal resistance is reduced, the capacity of the positive electrode material is improved, and the effect of improving the capacity of the battery is further achieved.
The weight ratio of the potassium permanganate to the graphitized mesocarbon microbeads is 1-3: 1, the potassium permanganate is high in oxidizing capacity, carbon on the surfaces of the graphitized mesocarbon microbeads can be oxidized to form graphene-like components, and the energy density of a negative electrode material is greatly improved.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that: the invention adopts LiFe1- xMnxPO4The PVDF with low molecular weight is used as the anode binder to reduce the rebound rate of the thickness of the anode plate as the high-voltage anode material, and the nano carbon plate/graphitized intermediate phase carbon microsphere composite material is used as the cathode material, so that the use of the cathode material is reduced by utilizing the high specific capacity of the cathode material, the thickness of the cathode plate is reduced, and the thickness of the battery is further reduced,the volume energy density of the battery is greatly improved; and the conductive film is added on the aluminum foil of the positive plate, so that the internal resistance of the battery can be effectively reduced, the energy loss of the battery in charging or discharging is reduced, and the utilization rate of the battery energy is improved.
[ detailed description ] embodiments
The present invention is further described in detail below with reference to specific examples and data tables.
Example 1
The invention relates to a high-voltage lithium ion battery with high volume energy density, which comprises a positive plate and a negative plate, wherein the positive plate comprises a positive material and a positive binder, and the negative plate comprises a negative material; the positive binder is PVDF, and the molecular weight of the positive binder is 30-50 ten thousand; the positive plate further comprises an aluminum foil, a conductive film is arranged between the positive material and the aluminum foil, and the thickness of the conductive film is 1-3 mu m. Before coating a positive electrode material on the positive electrode plate, firstly, attaching a layer of conductive film on an aluminum foil, wherein the conductive film can be composed of graphene and PVDF according to a weight ratio of 95:5, and is sprayed on the aluminum foil by static electricity; the negative electrode material is a nano carbon sheet/graphitized mesocarbon carbon microsphere composite material, and the nano carbon sheet is a three-dimensional graphene-like nanosheet.
The cathode material nano carbon sheet/graphitized mesocarbon microbead composite material is prepared from graphitized mesocarbon microbeads, and the preparation method comprises the following steps:
(1) adding 200mL of 98% concentrated sulfuric acid into a 1000mL clean round-bottom flask, controlling the reaction temperature of the flask to be 2 ℃, adding 8g of graphitized mesocarbon microbeads through mechanical stirring, slowly adding 1.0g of sodium nitrate for multiple times, finally slowly adding potassium permanganate for multiple times, and reacting for 2 hours;
(2) the reaction temperature is increased to 30 ℃, after stirring for 1 hour, 400mL of deionized water at 60 ℃ is added under the stirring condition, the heating temperature is increased to 85 ℃, and 150mL of H with the mass fraction of 10 percent is added2O2Continuously stirring for 3 hours, and finishing the reaction;
(3) washing once by using an HCl solution with the mass fraction of 10%, washing to be neutral by using deionized water, performing vacuum filtration, and drying in an oven at 80-100 ℃ to obtain a graphitized mesocarbon microbead intermediate;
(4) and (3) reducing the graphitized mesocarbon microbead intermediate at 800 ℃ under an anaerobic condition at high temperature to finally obtain the nano carbon sheet/graphitized mesocarbon microbead composite material.
In the preparation process of the cathode material, the weight ratio of potassium permanganate to graphitized mesocarbon microbeads is 1.25: 1.
Example 2
The invention relates to a high-voltage lithium ion battery with high volume energy density, which comprises a positive plate and a negative plate, wherein the positive plate comprises a positive material and a positive binder, and the negative plate comprises a negative material; the positive binder is PVDF, and the molecular weight of the positive binder is 50-70 ten thousand; the positive plate further comprises an aluminum foil, a conductive film is arranged between the positive material and the aluminum foil, and the thickness of the conductive film is 1-3 mu m. Before coating a positive electrode material on the positive electrode plate, firstly, attaching a layer of conductive film on an aluminum foil, wherein the conductive film can be composed of graphene and PVDF according to a weight ratio of 98:2, and is sprayed on the aluminum foil by static electricity; the negative electrode material is a nano carbon sheet/graphitized mesocarbon carbon microsphere composite material, and the nano carbon sheet is a three-dimensional graphene-like nanosheet.
The cathode material nano carbon sheet/graphitized mesocarbon microbead composite material is prepared from graphitized mesocarbon microbeads, and the preparation method comprises the following steps:
(1) adding 200mL of 98% concentrated sulfuric acid into a 1000mL clean round-bottom flask, controlling the reaction temperature of the flask to be 8 ℃, adding 8g of graphitized mesocarbon microbeads through mechanical stirring, slowly adding 4.0g of sodium nitrate for multiple times, finally slowly adding potassium permanganate for multiple times, and reacting for 5 hours;
(2) the reaction temperature is increased to 40 ℃, stirring is continued for 5 hours, 400mL of deionized water with the temperature of 100 ℃ is added under the stirring condition, the heating temperature is increased to 105 ℃, and 150mL of H with the mass fraction of 10 percent is added2O2Continuing stirring for 7 hours, and finishing the reaction;
(3) washing once by using an HCl solution with the mass fraction of 10%, washing to be neutral by using deionized water, performing vacuum filtration, and drying in an oven at 80-100 ℃ to obtain a graphitized mesocarbon microbead intermediate;
(4) and (3) reducing the graphitized mesocarbon microbead intermediate at high temperature of 1100 ℃ under an anaerobic condition to finally obtain the nano carbon sheet/graphitized mesocarbon microbead composite material.
In the preparation process of the cathode material, the weight ratio of potassium permanganate to graphitized mesocarbon microbeads is 1.75: 1.
Example 3
The invention relates to a high-voltage lithium ion battery with high volume energy density, which comprises a positive plate and a negative plate, wherein the positive plate comprises a positive material and a positive binder, and the negative plate comprises a negative material; the positive binder is PVDF, and the molecular weight of the positive binder is 50-70 ten thousand; the positive plate further comprises an aluminum foil, a conductive film is arranged between the positive material and the aluminum foil, and the thickness of the conductive film is 1-3 mu m. Before coating the positive electrode material on the positive electrode plate, a conductive film is attached to the aluminum foil, wherein the conductive film can be made of graphene, and the conductive film is attached to the aluminum foil by a vapor deposition method. The negative electrode material is a nano carbon sheet/graphitized mesocarbon carbon microsphere composite material, and the nano carbon sheet is a three-dimensional graphene-like nanosheet.
The cathode material nano carbon sheet/graphitized mesocarbon microbead composite material is prepared from graphitized mesocarbon microbeads, and the preparation method comprises the following steps:
(1) adding 200mL of 98% concentrated sulfuric acid into a 1000mL clean round-bottom flask, controlling the reaction temperature of the flask to be 5 ℃, adding 8g of graphitized mesophase carbon microspheres by mechanical stirring, slowly adding 2.5g of sodium nitrate for multiple times, finally slowly adding potassium permanganate for multiple times, and reacting for 3.5 hours;
(2) the reaction temperature is increased to 35 ℃, stirring is continued for 3 hours, 400mL of deionized water with the temperature of 80 ℃ is added under the stirring condition, the heating temperature is increased to 95 ℃, and 150mL of H with the mass fraction of 10 percent is added2O2Continuously stirring for 5 hours, and finishing the reaction;
(3) washing once by using an HCl solution with the mass fraction of 10%, washing to be neutral by using deionized water, performing vacuum filtration, and drying in an oven at 80-100 ℃ to obtain a graphitized mesocarbon microbead intermediate;
(4) and (3) reducing the graphitized mesocarbon microbead intermediate at high temperature under the anaerobic condition of 950 ℃ to finally obtain the nano carbon sheet/graphitized mesocarbon microbead composite material.
In the preparation process of the cathode material, the weight ratio of potassium permanganate to graphitized mesocarbon microbeads is 2.25: 1.
Effect verification:
an 856068 model lithium ion battery with the capacity of 4000mAh is taken as an example. The standard size of the battery cell is 7.6mm in thickness, 50.0mm in width and 68.0mm in length, and the standard volume energy density of the battery corresponding to the positive electrode material of lithium manganese iron phosphate is 426.7 Wh/L.
Experimental groups: the experimental group was tested by assembling batteries using the materials and compositions of examples 1-3, and the assembly process of the batteries was as follows:
(1) preparation of the positive electrode: lithium manganese iron phosphate is used as an anode active substance, super conductive carbon black (SP) is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a binder, and N-dimethyl pyrrolidone (NMP) is used as a solvent. The viscosity of the prepared slurry is controlled to be 2000-8500 mPa & s. The mass percentages of the lithium manganese iron phosphate used in the embodiment are as follows: SP: PVDF 97:1.4: 1.6. Firstly, fully dissolving PVDF in NMP to prepare a glue solution, continuously adding SP, uniformly stirring, finally adding lithium manganese iron phosphate, continuously uniformly stirring, vacuumizing, and removing bubbles in the slurry. Finally, the obtained slurry was uniformly coated on both sides on an aluminum foil having a thickness of 12 μm. After drying, rolling and cutting pieces, welding the tabs with the thickness of 0.1 mm. And finishing the manufacture of the positive plate.
(2) Preparation of a negative electrode: the self-made HGMCMB is taken as a negative active substance, the conductive agent is high-conductivity acetylene black, the binder is a composition of aqueous styrene-butadiene rubber emulsion SBR and sodium carboxymethylcellulose CMC, and water is taken as a solvent. The viscosity of the prepared slurry is controlled to be 1000-4500 mPas. The mass percentages used in this example are HGMCMB: AB: CMC: SBR-96.5: 1:1: 1.5. Fully dissolving CMC in water to prepare a glue solution, continuously adding AB and uniformly stirring, adding SBR and stirring for 1.5h after adding HGMCMB and continuously and uniformly stirring, vacuumizing and removing bubbles in the slurry. And finally, the obtained slurry is evenly coated on the copper foil with the thickness of 8 mu m on both sides. After drying, rolling and cutting pieces, welding the tabs with the thickness of 0.1 mm. And finishing the manufacture of the negative plate.
(3) Assembling the battery: the separator was a microporous polyethylene film having a thickness of 12 μm. The thickness of the plastic-aluminum film was 113. mu.m. And winding the prepared positive and negative plates and the diaphragm into a winding core, carrying out primary packaging, injecting liquid and packaging, and carrying out formation and secondary packaging to finish the manufacture of the battery.
Control group: the assembly test was performed with the same type of battery as the experimental group. The materials of the control group are lithium iron manganese phosphate and graphitized mesocarbon microbeads which are the same as those of the experimental group, when the positive plate is manufactured, the molecular weights of positive binders are 70-100 million and 100-120 million of PVDF respectively, the proportion and the dosage of the materials are the same as those of the experimental group, and the aluminum foil is directly coated with the positive material according to the conventional process without any conductive film attached, and the battery is assembled according to the experimental group.
For comparison, the other parameters of the control group were the same as those of the experimental group, and the specific results are shown in tables 1 and 2:
TABLE 1 thickness of rolled pole piece and rebound before winding
| The thickness/mm of the rolled positive pole piece | Negative pole piece thickness/mm after rolling | Thickness/mm of positive plate before winding | Thickness/mm of negative plate before winding | Positive plate rebound rate | |
| Example 1 | 0.194 | 0.089 | 0.201 | 0.105 | 3.61％ |
| Example 2 | 0.195 | 0.043 | 0.205 | 0.051 | 5.13％ |
| Example 3 | 0.194 | 0.027 | 0.203 | 0.032 | 4.64％ |
| Control group 1 | 0.195 | 0.112 | 0.210 | 0.131 | 7.69％ |
| Control group 2 | 0.195 | 0.112 | 0.223 | 0.130 | 14.36％ |
As can be seen from table 1: the larger the molecular weight of the positive binder PVDF is, the larger the rebound rate of the positive plate is, so that the plate is thicker, the overall thickness of the battery is influenced, and the volume energy density of the battery is further reduced; and the thickness of the negative plate is reduced along with the increase of the weight ratio of the potassium permanganate to the graphitized mesocarbon microbeads.
TABLE 2 comparison of cell parameters for control and experimental groups
As can be seen from tables 1 and 2: the battery prepared by using the nano carbon sheet/graphitized mesocarbon microbeads composite material has higher volume energy density than the battery prepared by using the graphitized mesocarbon microbeads, the needed negative electrode material is better, and the thickness of the negative electrode plate is thinner; in addition, the conductive film is added on the aluminum foil, so that the internal resistance of the battery can be reduced.
Claims (2)
1. A high-voltage lithium ion battery with high volume energy density comprises a positive plate and a negative plate, wherein the positive plate comprises a positive material and a positive binder, and the negative plate comprises a negative material, and is characterized in that the positive material is lithium manganese iron phosphate, and the iron-manganese ratio of the lithium manganese iron phosphate is 0.1-0.35: 0.65-0.90; the positive electrode binder is PVDF, and the molecular weight of the positive electrode binder is 30 ten thousand; the negative electrode material is a nano carbon sheet/graphitized mesocarbon carbon microsphere composite material, and the nano carbon sheet is a three-dimensional graphene-like nanosheet;
the positive plate further comprises an aluminum foil, a conductive film is arranged between the positive material and the aluminum foil, and the thickness of the conductive film is 1-3 mu m;
the conductive film is composed of graphene and PVDF according to a weight ratio of 95-98: 2-5, and is sprayed on an aluminum foil through static electricity;
the preparation method of the nano carbon sheet/graphitized mesocarbon microbead composite material comprises the following steps:
(1) adding 200mL of 98% concentrated sulfuric acid into a 1000mL clean round-bottom flask, controlling the reaction temperature of the flask to be 2-8 ℃, adding 8g of graphitized mesocarbon microbeads through mechanical stirring, slowly adding 1.0-4.0 g of sodium nitrate for multiple times, finally slowly adding potassium permanganate for multiple times, and reacting for 2-5 hours;
(2) raising the reaction temperature to 30-40 ℃, continuously stirring for 1-5H, adding 400mL of deionized water at 60-100 ℃ under the stirring condition, raising the heating temperature to 85-105 ℃, and adding 150mL of H with the mass fraction of 10%2O2Continuously stirring for 3-7 h, and finishing the reaction;
(3) washing once by using an HCl solution with the mass fraction of 10%, washing to be neutral by using deionized water, performing vacuum filtration, and drying in an oven at 80-100 ℃ to obtain a graphitized mesocarbon microbead intermediate;
(4) and (3) reducing the graphitized intermediate phase carbon microsphere intermediate at 800-1100 ℃ under an anaerobic condition at high temperature to finally obtain the nano carbon sheet/graphitized intermediate phase carbon microsphere composite material.
2. The high-voltage lithium ion battery with high volumetric energy density according to claim 1, wherein the weight ratio of the potassium permanganate to the graphitized mesocarbon microbeads is 1-3: 1.
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