CN108598367B - High-voltage negative plate, preparation method thereof and high-voltage lithium battery - Google Patents

High-voltage negative plate, preparation method thereof and high-voltage lithium battery Download PDF

Info

Publication number
CN108598367B
CN108598367B CN201810385887.9A CN201810385887A CN108598367B CN 108598367 B CN108598367 B CN 108598367B CN 201810385887 A CN201810385887 A CN 201810385887A CN 108598367 B CN108598367 B CN 108598367B
Authority
CN
China
Prior art keywords
current collector
positive
negative
aluminum alloy
alloy foil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810385887.9A
Other languages
Chinese (zh)
Other versions
CN108598367A (en
Inventor
姚学永
易辉华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Yongbang New Energy Co
Original Assignee
Guangdong Yongbang New Energy Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Yongbang New Energy Co filed Critical Guangdong Yongbang New Energy Co
Priority to CN201810385887.9A priority Critical patent/CN108598367B/en
Publication of CN108598367A publication Critical patent/CN108598367A/en
Application granted granted Critical
Publication of CN108598367B publication Critical patent/CN108598367B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

Abstract

The invention relates to the technical field of lithium batteries, in particular to a high-voltage negative plate, a preparation method thereof and a high-voltage lithium battery, wherein the high-voltage negative plate comprises a negative current collector and a negative slurry layer coated on the surface of the negative current collector, and is characterized in that: the negative electrode slurry layer is prepared by carbonizing 50-70 wt% of cellulose, 29-47 wt% of graphene and 1-3 wt% of first binder. According to the invention, the graphene is used as one of the active substances of the negative plate of the lithium battery, so that the lithium storage capacity of the battery can be greatly improved, the energy density is further improved, the conductive network structure of the negative slurry layer is improved through carbonization, the lithium intercalation-deintercalation is facilitated, the use amount of the graphene is reduced, and the cost is reduced.

Description

High-voltage negative plate, preparation method thereof and high-voltage lithium battery
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a high-voltage negative plate, a preparation method thereof and a high-voltage lithium battery.
Background
With the rapid development of electronic devices and the increasingly prominent energy and environmental issues, people have made higher demands on chemical power sources. The lithium ion battery rapidly rises in the market by the advantages of high voltage, large specific energy, long cycle life, no pollution and the like, and becomes a novel clean and high-energy source. Particularly, in the twenty-first century, the rapid development and wide application of various portable electronic devices, wireless mobile communication devices and electric vehicles are more urgent for the demand of lithium ion batteries with higher specific capacity, long cycle service life and low cost.
The key to improving the high specific energy index of the lithium ion battery lies in the development of the high specific energy positive electrode active material, and most researchers put major efforts into the development of the high specific energy positive electrode active material and neglect the design of the negative electrode.
The negative electrode of the lithium ion battery is formed by uniformly coating a paste adhesive prepared by mixing a negative electrode active material carbon material or non-carbon material, a binder and an additive on two sides of a copper foil, drying and rolling. The key to successful production of lithium ion batteries is the ability to produce negative electrode materials that reversibly deintercalate/intercalate lithium ions. At present, the negative electrode material that has been practically used in lithium ion batteries is generally a carbon material such as graphite, soft carbon (e.g., coke, etc.), hard carbon, and the like. The negative electrode materials being searched for include nitrides, PAS, tin-based oxides, tin alloys, nano-negative electrode materials, and other intermetallic compounds. Therefore, the specific capacity and cycle life of the lithium ion battery can be improved by improving the negative active material, and the cost of the lithium ion battery can be reduced by developing a novel negative active material.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a high-voltage negative plate with high specific capacity, long cycle service life and low cost, and the invention also aims to provide a preparation method of the high-voltage negative plate, which can improve the layered structure of graphene in the carbonization process of cellulose through coating and carbonizing, and is more suitable for lithium intercalation-deintercalation.
The purpose of the invention is realized by the following technical scheme:
the high-voltage negative plate comprises a negative current collector and a negative slurry layer coated on the surface of the negative current collector, wherein the negative slurry layer is prepared by carbonizing 50-70 wt% of cellulose, 29-47 wt% of graphene and 1-3 wt% of first binder.
Wherein the length of the cellulose is 20-60 μm, the diameter is 200-300nm, the average particle size of the graphene is 30-80nm, and the BET surface area is 300-700m2(ii) in terms of/g. By controlling various parameters of the cellulose and the graphene, the dispersibility and the conductivity of the cellulose and the graphene can be effectively improved, a more stable conductive network structure can be formed after the cellulose is carbonized, the compaction density is improved, and the cycle performance of the negative plate is improved
The first binder is one or a mixture of polyvinylidene fluoride and polytetrafluoroethylene.
The invention also provides a preparation method of the high-voltage negative plate, which comprises the following steps: mixing cellulose, graphene and a first binder in a certain amount of organic solvent according to a ratio to form negative electrode slurry, coating the negative electrode slurry on the negative electrode current collector, drying, and performing high-temperature carbonization for 0.5-2h in an inert gas atmosphere at 1000-1400 ℃ to obtain the high-voltage negative electrode plate. The structure generation of the conductive network can be effectively controlled by controlling the carbonization time and the carbonization temperature, so that the energy density of the negative plate is improved.
The invention also provides a high-voltage lithium battery which comprises the positive plate, electrolyte, a diaphragm and the high-voltage negative plate.
The positive plate comprises a positive current collector and a positive slurry layer coated on the surface of the positive current collector, wherein the positive slurry layer consists of 87-95 wt% of positive active material, 4-10 wt% of conductive agent and 1-3 wt% of second binder, and the positive active material is LiNixCoyMnzO2Wherein x is more than or equal to 0.26 and less than or equal to 0.33, y is more than or equal to 0.44 and less than or equal to 0.61, z is more than or equal to 0.06 and less than or equal to 0.3, and x + y + z is 1. In the present application Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2、LiOH·H2The novel nickel-cobalt-manganese composite oxide is prepared by adopting a coprecipitation method by using O as a raw material, has the characteristics of low cost, high point position and strong stability, and can effectively improve the specific capacity of the nickel-cobalt-manganese composite oxide.
Wherein the conductive agent consists of carbon nano tubes and conductive graphite according to the weight ratio of 2-3: 1.
Wherein the second binder is polyvinylidene fluoride.
The positive current collector is prepared by carrying out corrosion treatment on aluminum alloy foil, and the aluminum alloy foil comprises the following components:
Figure BDA0001642216080000031
the balance being aluminum and unavoidable impurities.
The aluminum alloy foil has good mechanical property, the tensile strength is up to 200-220MPa, and meanwhile, due to the high content of Fe element, the aluminum alloy foil can generate porous property when being formed, so that the adhesion of the anode active substance and the conductive agent is facilitated, the powder falling phenomenon is not easy to generate, and the cycle performance is good; the porous alloy foil also has larger specific surface area and higher conductive efficiency, thereby improving the discharge specific capacity of the invention.
Further, the preparation method of the positive electrode current collector comprises the following steps: A. preparing aluminum alloy foil: weighing a metal simple substance or an intermediate alloy according to the component proportion of the aluminum alloy foil, and sequentially carrying out smelting, homogenization treatment, cold rolling and two-stage aging to obtain the aluminum alloy foil; B. and (3) corrosion treatment: carrying out direct current energization on the aluminum alloy foil, wherein the current density is 0.1-0.2A/cm2And placing the aluminum alloy foil in HCl solution with the concentration of 0.05-0.2mol/L for corrosion for 7-10min, and then cleaning with deionized water and absolute ethyl alcohol to obtain the anode current collector. Through further corrosion treatment, the porosity of the aluminum alloy foil can be more remarkable, the porosity and the suitable micropore diameter are realized, and the conductive efficiency and the adhesive force of the anode slurry layer are favorably improved.
Further, the smelting temperature is 720-740 ℃, the homogenization treatment temperature is 600-660 ℃, the homogenization treatment time is 4-8h, the two-stage aging is heat preservation at 140 ℃ for 10-14h and at 200 ℃ for 30-50 min. By controlling the preparation parameters of the aluminum alloy foil, the aluminum alloy foil can have proper mechanical properties and conductivity.
Wherein the pore diameter of the micropores on the surface of the positive current collector is 20-60 μm, the porosity of the positive current collector is 18-22%, and the thickness of the positive current collector is 6-20 μm.
The invention has the beneficial effects that: 1. according to the invention, the graphene is used as one of the active substances of the negative electrode plate of the lithium battery, so that the lithium storage capacity of the battery can be greatly improved, and the energy density is further improved; 2. according to the invention, the graphene is subjected to blending modification by adopting cellulose, and then the conductive network structure of the negative slurry layer is improved through carbonization, so that the lithium intercalation-deintercalation is facilitated, the use amount of the graphene is reduced, and the cost is reduced; 3. the cellulose can play a role in bonding when forming the negative electrode slurry and coating the negative electrode slurry on the negative electrode current collector, so that the use of a binder can be reduced, and then the cellulose is converted into carbon fibers with good conductivity through high-temperature carbonization, so that the negative electrode slurry layer has a good conductive structure and is not easy to remove powder; 4. the lithium battery manufactured by the high-voltage negative plate has the advantages of high specific capacity, long cycle service life, low cost and the like.
Drawings
FIG. 1 is a schematic diagram of a cycle of a battery according to example 1;
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and the accompanying fig. 1, and the description of the embodiments is not intended to limit the present invention.
Example 1
The high-voltage negative plate comprises a negative current collector and a negative slurry layer coated on the surface of the negative current collector, wherein the negative slurry layer is prepared by carbonizing 60 wt% of cellulose, 38 wt% of graphene and 2 wt% of first binder.
Wherein the cellulose has a length of 40 μm and a diameter of 250nm, the graphene has an average particle size of 55nm and a BET surface area of 500m2/g。
Wherein the first binder is polyvinylidene fluoride.
The invention also provides a preparation method of the high-voltage negative plate, which comprises the following steps: mixing cellulose, graphene and a first binder in 10 times of N-methyl pyrrolidone according to a ratio to form negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, drying, and performing high-temperature carbonization for 1.2h in an inert gas atmosphere of 1200 ℃ to obtain the high-voltage negative electrode sheet.
The invention also provides a high-voltage lithium battery which comprises the positive plate, electrolyte, a diaphragm and the high-voltage negative plate.
The positive plate comprises a positive current collector and a positive slurry layer coated on the surface of the positive current collector, wherein the positive slurry layer consists of 91 wt% of positive active substance, 7 wt% of conductive agent and 2 wt% of second binder, and the positive active substance is LiNixCoyMnzO2Wherein x is 0.3, y is 0.5, and z is 0.2.
The conductive agent is composed of carbon nanotubes and conductive graphite according to the weight ratio of 2.5: 1.
Wherein the second binder is polyvinylidene fluoride.
The positive current collector is prepared by carrying out corrosion treatment on aluminum alloy foil, and the aluminum alloy foil comprises the following components:
Figure BDA0001642216080000051
Figure BDA0001642216080000061
the balance being aluminum and unavoidable impurities.
Further, the preparation method of the positive electrode current collector comprises the following steps: A. preparing aluminum alloy foil: weighing a metal simple substance or an intermediate alloy according to the component proportion of the aluminum alloy foil, and sequentially carrying out smelting, homogenization treatment, cold rolling and two-stage aging to obtain the aluminum alloy foil; B. and (3) corrosion treatment: subjecting the aluminum alloy foil to DC energization with a current density of 0.15A/cm2And placing the aluminum alloy foil in HCl solution with the concentration of 0.12mol/L for corrosion for 8.5min, and then cleaning with deionized water and absolute ethyl alcohol to obtain the anode current collector.
Further, the smelting temperature is 730 ℃, the homogenization treatment temperature is 630 ℃, the homogenization treatment time is 6h, and the two-stage aging is heat preservation at 130 ℃ for 12h, and then heat preservation at 190 ℃ for 40 min.
The pore diameter of the micropores on the surface of the positive current collector is 40 micrometers, the porosity of the positive current collector is 20%, and the thickness of the positive current collector is 13 micrometers.
Example 2
The high-voltage negative plate comprises a negative current collector and a negative slurry layer coated on the surface of the negative current collector, wherein the negative slurry layer is prepared by carbonizing 50 wt% of cellulose, 47 wt% of graphene and 3 wt% of first binder.
Wherein the cellulose has a length of 20 μm and a diameter of 200nm, the graphene has an average particle size of 30nm and a BET surface area of 700m2/g。
Wherein the first binder is polyvinylidene fluoride.
The invention also provides a preparation method of the high-voltage negative plate, which comprises the following steps: mixing cellulose, graphene and a first binder in 10 times of N-methyl pyrrolidone according to a ratio to form negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, drying, and performing high-temperature carbonization for 2 hours in an inert gas atmosphere at 1000 ℃ to obtain the high-voltage negative electrode plate.
The invention also provides a high-voltage lithium battery which comprises the positive plate, electrolyte, a diaphragm and the high-voltage negative plate.
The positive plate comprises a positive current collector and a positive slurry layer coated on the surface of the positive current collector, wherein the positive slurry layer consists of 87 wt% of positive active substance, 10 wt% of conductive agent and 3 wt% of second binder, and the positive active substance is LiNixCoyMnzO2Wherein x is 0.26, y is 0.44, and z is 0.3.
The conductive agent is composed of carbon nanotubes and conductive graphite according to the weight ratio of 2: 1.
Wherein the second binder is polyvinylidene fluoride.
The positive current collector is prepared by carrying out corrosion treatment on aluminum alloy foil, and the aluminum alloy foil comprises the following components:
Figure BDA0001642216080000071
the balance being aluminum and unavoidable impurities.
Further, the preparation method of the positive electrode current collector comprises the following steps: A. preparing aluminum alloy foil: weighing a metal simple substance or an intermediate alloy according to the component proportion of the aluminum alloy foil, and sequentially carrying out smelting, homogenization treatment, cold rolling and two-stage aging to obtain the aluminum alloy foil; B. and (3) corrosion treatment: subjecting the aluminum alloy foil to DC energization with a current density of 0.1A/cm2And placing the aluminum alloy foil in HCl solution with the concentration of 0.05mol/L for corrosion for 7min, and then cleaning with deionized water and absolute ethyl alcohol to obtain the anode current collector.
Further, the smelting temperature is 720 ℃, the homogenization treatment temperature is 600 ℃, the homogenization treatment time is 4h, and the two-stage aging is heat preservation at 120 ℃ for 10h, and then heat preservation at 180 ℃ for 30 min.
The aperture of the micropores on the surface of the positive current collector is 20 microns, the porosity of the positive current collector is 18%, and the thickness of the positive current collector is 6 microns.
Example 3
The high-voltage negative plate comprises a negative current collector and a negative slurry layer coated on the surface of the negative current collector, wherein the negative slurry layer is prepared by carbonizing 70 wt% of cellulose, 29 wt% of graphene and 1 wt% of first binder.
Wherein the cellulose has a length of 60 μm and a diameter of 300nm, the graphene has an average particle size of 80nm and a BET surface area of 300m2/g。
Wherein the first binder is polyvinylidene fluoride.
The invention also provides a preparation method of the high-voltage negative plate, which comprises the following steps: mixing cellulose, graphene and a first binder in 10 times of N-methyl pyrrolidone according to a ratio to form negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, drying, and performing high-temperature carbonization for 0.5h in an inert gas atmosphere at 1400 ℃ to obtain the high-voltage negative electrode sheet.
The invention also provides a high-voltage lithium battery which comprises the positive plate, electrolyte, a diaphragm and the high-voltage negative plate.
The positive plate comprises a positive current collector and a positive slurry layer coated on the surface of the positive current collector, wherein the positive slurry layer consists of 95 wt% of positive active material, 4 wt% of conductive agent and 1 wt% of second binder, and the positive active material is LiNixCoyMnzO2Wherein x is 0.33, y is 0.61, and z is 0.6.
The conductive agent is composed of carbon nanotubes and conductive graphite according to the weight ratio of 3: 1.
Wherein the second binder is polyvinylidene fluoride.
The positive current collector is prepared by carrying out corrosion treatment on aluminum alloy foil, and the aluminum alloy foil comprises the following components:
Figure BDA0001642216080000091
the balance being aluminum and unavoidable impurities.
Further, the preparation method of the positive electrode current collector comprises the following steps: A. preparing aluminum alloy foil: weighing a metal simple substance or an intermediate alloy according to the component proportion of the aluminum alloy foil, and sequentially carrying out smelting, homogenization treatment, cold rolling and two-stage aging to obtain the aluminum alloy foil; B. and (3) corrosion treatment: subjecting the aluminum alloy foil to DC energization with a current density of 0.2A/cm2And placing the aluminum alloy foil in HCl solution with the concentration of 0.2mol/L for corrosion for 10min, and then cleaning with deionized water and absolute ethyl alcohol to obtain the anode current collector.
Further, the smelting temperature is 740 ℃, the homogenization treatment temperature is 660 ℃, the homogenization treatment time is 8h, and the double-stage aging is heat preservation at 140 ℃ for 14h, and then heat preservation at 200 ℃ for 50 min.
The pore diameter of the micropores on the surface of the positive current collector is 60 micrometers, the porosity of the positive current collector is 22%, and the thickness of the positive current collector is 20 micrometers.
Example 4
The high-voltage negative plate comprises a negative current collector and a negative slurry layer coated on the surface of the negative current collector, wherein the negative slurry layer is prepared by carbonizing 55 wt% of cellulose, 43.5 wt% of graphene and 1.5 wt% of first binder.
Wherein the cellulose has a length of 30 μm and a diameter of 220nm, the graphene has an average particle size of 40nm and a BET surface area of 600m2/g。
The first binder is composed of polyvinylidene fluoride and polytetrafluoroethylene according to the weight ratio of 1: 1.
The invention also provides a preparation method of the high-voltage negative plate, which comprises the following steps: mixing cellulose, graphene and a first binder in 10 times of N-methyl pyrrolidone according to a ratio to form negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, drying, and performing high-temperature carbonization for 1.5h in an inert gas atmosphere at 1100 ℃ to obtain the high-voltage negative electrode sheet.
The invention also provides a high-voltage lithium battery which comprises the positive plate, electrolyte, a diaphragm and the high-voltage negative plate.
The positive plate comprises a positive current collector and a positive slurry layer coated on the surface of the positive current collector, wherein the positive slurry layer consists of 90 wt% of positive active material, 7 wt% of conductive agent and 3 wt% of second binder, and the positive active material is LiNixCoyMnzO2Wherein x is 0.28, y is 0.55, and z is 0.17.
The conductive agent is composed of carbon nanotubes and conductive graphite according to the weight ratio of 2.2: 1.
Wherein the second binder is polyvinylidene fluoride.
The positive current collector is prepared by carrying out corrosion treatment on aluminum alloy foil, and the aluminum alloy foil comprises the following components:
Figure BDA0001642216080000101
the balance being aluminum and unavoidable impurities.
Further, the preparation method of the positive electrode current collector comprises the following steps: A. preparing aluminum alloy foil: weighing a metal simple substance or an intermediate alloy according to the component proportion of the aluminum alloy foil, and sequentially carrying out smelting, homogenization treatment, cold rolling and two-stage aging to obtain the aluminum alloy foil; B. and (3) corrosion treatment: subjecting the aluminum alloy foil to DC energization with a current density of 0.13A/cm2And placing the aluminum alloy foil in HCl solution with the concentration of 0.1mol/L for corrosion for 8min, and then cleaning with deionized water and absolute ethyl alcohol to obtain the anode current collector.
Further, the smelting temperature is 725 ℃, the homogenization treatment temperature is 620 ℃, the homogenization treatment time is 5 hours, and the double-stage aging is heat preservation at 125 ℃ for 11 hours, and then heat preservation at 185 ℃ for 35 minutes.
The pore diameter of the micropores on the surface of the positive current collector is 30 micrometers, the porosity of the positive current collector is 19%, and the thickness of the positive current collector is 10 micrometers.
Example 5
The high-voltage negative plate comprises a negative current collector and a negative slurry layer coated on the surface of the negative current collector, wherein the negative slurry layer is prepared by carbonizing 65 wt% of cellulose, 32.5 wt% of graphene and 2.5 wt% of first binder.
Wherein the cellulose has a length of 50 μm and a diameter of 280nm, the graphene has an average particle size of 70nm and a BET surface area of 400m2/g。
Wherein the first binder is polytetrafluoroethylene.
The invention also provides a preparation method of the high-voltage negative plate, which comprises the following steps: mixing cellulose, graphene and a first binder in 10 times of N-methyl pyrrolidone according to a ratio to form negative electrode slurry, coating the negative electrode slurry on a negative electrode current collector, drying, and performing high-temperature carbonization for 1h in an inert gas atmosphere at 1300 ℃ to obtain the high-voltage negative electrode plate.
The invention also provides a high-voltage lithium battery which comprises the positive plate, electrolyte, a diaphragm and the high-voltage negative plate.
The positive plate comprises a positive current collector and a positive slurry layer coated on the surface of the positive current collector, wherein the positive slurry layer consists of 93 wt% of positive active material, 4.5 wt% of conductive agent and 2.5 wt% of second binder, and the positive active material is LiNixCoyMnzO2Wherein x is 0.32, y is 0.45, and z is 0.23.
Wherein the conductive agent consists of carbon nano tubes and conductive graphite according to the weight ratio of 2.7: 1.
Wherein the second binder is polyvinylidene fluoride.
The positive current collector is prepared by carrying out corrosion treatment on aluminum alloy foil, and the aluminum alloy foil comprises the following components:
Figure BDA0001642216080000121
the balance being aluminum and unavoidable impurities.
Further, the preparation method of the positive electrode current collector comprises the following steps: A. preparing aluminum alloy foil: weighing a metal simple substance or an intermediate alloy according to the component proportion of the aluminum alloy foil, and sequentially carrying out smelting, homogenization treatment, cold rolling and two-stage aging to obtain the aluminum alloy foil; B. and (3) corrosion treatment: subjecting the aluminum alloy foil to DC energization with a current density of 0.18A/cm2Placing the aluminum alloy foil in HCl solution with the concentration of 0.15mol/L for corrosion for 9min, and then cleaning with deionized water and absolute ethyl alcohol to obtain the anode setA fluid.
Further, the smelting temperature is 735 ℃, the homogenization treatment temperature is 650 ℃, the homogenization treatment time is 7h, and the two-stage aging is heat preservation at 135 ℃ for 13h, and then heat preservation at 195 ℃ for 45 min.
The aperture of the micropores on the surface of the positive current collector is 50 microns, the porosity of the positive current collector is 21%, and the thickness of the positive current collector is 15 microns.
Comparative example 1
The lithium battery of this comparative example differs from example 1 in that: the negative electrode slurry layer was composed of 98 wt% of conductive graphite and 2 wt% of a binder.
Example 6 Performance testing
The lithium batteries of examples 1 to 5 and comparative example 1 were charged to 4.5V at a constant current of 0.1C, charged to a current of 0.05C at a constant voltage of 4.5V, left to stand for 5min, and discharged to 3.0V at a constant current of 0.1C, and the specific capacity of the initial discharge was recorded.
The battery was cycled between 3.0V and 4.5V, charged and discharged at 1C rate, and the capacity retention rate was recorded over 400 cycles of the battery, and the cycle life curve of example 1 was recorded, as shown in fig. 1.
The data recorded are as follows:
specific capacity of first cycle discharge (mAh/g) Capacity retention (%) after 400 cycles
Example 1 192.1 85.8
Example 2 189.6 82.7
Example 3 189.7 82.3
Example 4 186.5 78.5
Example 5 186.6 78.9
Comparative example 1 178.4 73.6
As can be seen from the above table and fig. 1, the lithium battery of the present invention has excellent specific capacity and cycle performance, and as can be seen from the comparison between example 1 and comparative example 1, the present invention greatly improves the specific discharge capacity and cycle performance by improving the composition of the negative electrode slurry layer, and has characteristics of high voltage (3.0V to 4.5V), and also has low cost and extremely high industrial production value due to the adoption of cellulose with low cost as the negative electrode active material.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.

Claims (3)

1. The utility model provides a high voltage lithium cell, includes positive plate, electrolyte, diaphragm, its characterized in that:
the high-voltage negative plate is also included; the high-voltage negative plate comprises a negative current collector and a negative slurry layer coated on the surface of the negative current collector, wherein the negative slurry layer is prepared by carbonizing 50-70 wt% of cellulose, 29-47 wt% of graphene and 1-3 wt% of first binder; the length of the cellulose is 20-60 mu m, the diameter is 200-300nm, the average particle size of the graphene is 30-80nm, and the BET surface area is 300-700 square meters per gram; the first binder is one or a mixture of polyvinylidene fluoride and polytetrafluoroethylene;
the preparation method of the high-voltage negative plate comprises the following steps: mixing cellulose, graphene and a first binder in a certain amount of organic solvent according to a ratio to form negative electrode slurry, coating the negative electrode slurry on the negative electrode current collector, drying, and performing high-temperature carbonization for 0.5-2h in an inert gas atmosphere at the temperature of 1000-1400 ℃ to obtain the high-voltage negative electrode plate;
the positive plate comprises a positive current collector and a positive slurry layer coated on the surface of the positive current collector, wherein the positive slurry layer consists of 87 wt% -95 wt% of positive active substance, 4 wt% -10 wt% of conductive agent and 1 wt% -3 wt% of second binder, and the positive active substance is LiNixCoyMnzO2Wherein x is more than or equal to 0.26 and less than or equal to 0.33, y is more than or equal to 0.44 and less than or equal to 0.61, z is more than or equal to 0.06 and less than or equal to 0.3, and x + y + z is equal to 1;
the positive current collector is prepared by carrying out corrosion treatment on aluminum alloy foil, and the aluminum alloy foil comprises the following components:
Figure FDA0002638902830000011
the balance of aluminum and inevitable impurities;
the preparation method of the positive current collector comprises the following steps: A. preparing aluminum alloy foil: weighing a metal simple substance or an intermediate alloy according to the component proportion of the aluminum alloy foil, and sequentially carrying out smelting, homogenization treatment, cold rolling and two-stage aging to obtain the aluminum alloy foil;
B. and (3) corrosion treatment:carrying out direct current energization on the aluminum alloy foil, wherein the current density is 0.1-0.2A/cm2Placing the aluminum alloy foil in HCl solution with the concentration of 0.05-0.2mol/L for corrosion for 7-10min, and then cleaning with deionized water and absolute ethyl alcohol to obtain a positive current collector;
the pore diameter of the micropores on the surface of the positive current collector is 20-60 mu m, the porosity of the positive current collector is 18-22%, and the thickness of the positive current collector is 6-20 mu m.
2. A high voltage lithium battery as claimed in claim 1, characterized in that: the conductive agent is composed of carbon nano tubes and conductive graphite according to the weight ratio of 2-3: 1.
3. A high voltage lithium battery as claimed in claim 1, characterized in that: the smelting temperature is 720-740 ℃, the homogenization treatment temperature is 600-660 ℃, the homogenization treatment time is 4-8h, the two-stage aging is heat preservation at 140 ℃ for 10-14h and at 200 ℃ for 30-50 min.
CN201810385887.9A 2018-04-26 2018-04-26 High-voltage negative plate, preparation method thereof and high-voltage lithium battery Active CN108598367B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810385887.9A CN108598367B (en) 2018-04-26 2018-04-26 High-voltage negative plate, preparation method thereof and high-voltage lithium battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810385887.9A CN108598367B (en) 2018-04-26 2018-04-26 High-voltage negative plate, preparation method thereof and high-voltage lithium battery

Publications (2)

Publication Number Publication Date
CN108598367A CN108598367A (en) 2018-09-28
CN108598367B true CN108598367B (en) 2020-12-08

Family

ID=63610258

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810385887.9A Active CN108598367B (en) 2018-04-26 2018-04-26 High-voltage negative plate, preparation method thereof and high-voltage lithium battery

Country Status (1)

Country Link
CN (1) CN108598367B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109461881B (en) * 2018-10-17 2020-07-03 宁德时代新能源科技股份有限公司 Negative pole piece and secondary battery
CN114447284B (en) * 2022-01-13 2024-04-05 东莞市无中有新能源科技有限公司 Preparation method of graphene negative plate and lithium battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101510625A (en) * 2009-03-26 2009-08-19 西安瑟福能源科技有限公司 Ultra-high magnification lithium ion battery
CN102245788A (en) * 2009-03-05 2011-11-16 东洋铝株式会社 Aluminum alloy foil for current collector and method for producing the same
WO2016025532A1 (en) * 2014-08-11 2016-02-18 The Arizona Board Of Regents On Behalf Of The University Of Arizona Aligned graphene-carbon nanotube porous carbon composite

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102245788A (en) * 2009-03-05 2011-11-16 东洋铝株式会社 Aluminum alloy foil for current collector and method for producing the same
CN101510625A (en) * 2009-03-26 2009-08-19 西安瑟福能源科技有限公司 Ultra-high magnification lithium ion battery
WO2016025532A1 (en) * 2014-08-11 2016-02-18 The Arizona Board Of Regents On Behalf Of The University Of Arizona Aligned graphene-carbon nanotube porous carbon composite

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Green fabrication of cellulose/graphene composite in ionic liquid and its electrochemical and photothermal properties";Weijie Ye et al.;《Chemical Engineering Journal》;20160416;摘要，第46页第2栏-第47页第1栏，第52页第1栏，图1、7 *
"Green fabrication of cellulose/graphene composite in ionic liquid and its electrochemical and photothermal properties";Weijie Ye;《Chemcial Engineering Journal》;20160416;摘要，第46页第2栏-第47页第1栏，第52页第1栏，图1、7 *

Also Published As

Publication number Publication date
CN108598367A (en) 2018-09-28

Similar Documents

Publication Publication Date Title
CN110620223B (en) Lithium ion battery pre-lithiation silicon-carbon multilayer composite negative electrode material and preparation method thereof
CN108493400B (en) High-voltage positive plate and preparation method thereof
CN101894940B (en) Preparation method of porous silicon-based cathode for lithium battery
AU2011349121B2 (en) Electrode and electrical storage device for lead-acid system
CN109860526B (en) Preparation method of graphite material doped with metal oxalate lithium battery composite negative electrode material
CN110048126B (en) Manufacturing process of aluminum foil and positive current collector
CN108584944A (en) A kind of preparation method of the ultracapacitor rich nitrogen grading porous carbon electrode material of high-specific surface area
CN108598367B (en) High-voltage negative plate, preparation method thereof and high-voltage lithium battery
CN109546099B (en) Graphite composite negative electrode material, preparation method thereof and lithium ion battery
CN111705315B (en) Preparation method of modified copper three-dimensional framework and application of modified copper three-dimensional framework in lithium battery
CN111952585A (en) High-compaction-density rubidium-doped lithium battery positive electrode material and preparation method thereof
CN114408919B (en) Porous carbon material based on high-temperature thermal shock carbonization and KOH activation of coconut shell material, preparation method and application
CN112607735B (en) Nitrogen/sulfur co-doped porous carbon material and preparation method and application thereof
CN115172680A (en) High-capacity high-rate lithium ion battery and preparation method thereof
CN111224197B (en) Lithium fluorocarbon-supercapacitor quick response composite battery
CN113258050A (en) Five-element high-entropy alloy oxide negative electrode material and preparation method and application thereof
CN108455685B (en) kinds of N/Co3O4Preparation method of porous composite material
CN112786834A (en) Positive pole piece and lithium ion battery comprising same
CN108011090B (en) Method for preparing lithium ion battery cathode, battery cathode prepared by method and lithium ion battery
JP2010257673A (en) Lead storage battery
CN111847526A (en) High-capacity super capacitor
CN112700967B (en) Cu with high specific capacity2-xNegative electrode material of Se super capacitor
CN113582250B (en) Preparation method of layered structure nickel cobaltate-nitrogen-containing graphene composite material, application of layered structure nickel cobaltate-nitrogen-containing graphene composite material in super capacitor and test method
CN108257792B (en) High-thermal-conductivity graphene composite membrane and preparation method and application thereof
CN110391423B (en) Lead-carbon battery positive grid, preparation method thereof and lead-carbon battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant