CN110661031A - Double-graphite electrode battery - Google Patents

Double-graphite electrode battery Download PDF

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Publication number
CN110661031A
CN110661031A CN201910859658.0A CN201910859658A CN110661031A CN 110661031 A CN110661031 A CN 110661031A CN 201910859658 A CN201910859658 A CN 201910859658A CN 110661031 A CN110661031 A CN 110661031A
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graphite
battery
double
lithium
negative
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唐联兴
郑正坤
刘右军
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Dongguan Lilong Battery Technology Co Ltd
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Dongguan Lilong Battery Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a double-graphite electrode battery, which comprises a positive plate, a negative plate, electrolyte and a diaphragm which is arranged between the positive plate and the negative plate at intervals, wherein a positive active material of the positive plate is graphite or amorphous carbon-coated graphite; the negative active material of the negative plate is graphite or amorphous carbon-coated graphite; the working voltage of the battery is 4.5-5.5V. Compared with the prior art, the positive electrode and the negative electrode of the double-graphite battery both adopt graphite as active materials, particularly, the graphite capable of being embedded with electrolyte salt anions replaces the traditional positive electrode material, the electrolyte salt anions are embedded into the positive electrode of the graphite under high voltage, and lithium ions are embedded into the negative electrode of the graphite to form a loop, so that the double-graphite battery is complete. The battery does not contain transition metal elements, is environment-friendly, can meet the use requirements in the fields of solar energy, wind energy, tidal energy and the like, and effectively reduces the manufacturing cost of the battery by adopting graphite as an active material.

Description

Double-graphite electrode battery
Technical Field
The invention relates to the field of lithium batteries, in particular to a double-graphite-electrode battery.
Background
At present, the lithium ion battery is mainly applied to mobile electronic products and automobile battery markets, but due to the defects of the cycle life, safety and cost, the lithium ion battery is not an ideal choice in broader markets with strategic significance, such as the fields of solar energy, wind energy, tidal energy and the like. In these application scenarios, energy density is no longer a major concern, compared to environmental impact and cost control, which is a concern in this field.
While transition metal is an indispensable element in the conventional lithium ion battery, particularly for the cathode material, the main choice of the cathode material is a transition metal oxide capable of reversibly removing and inserting lithium, such as common LiCoO2、LiMn2O4And LiFePO4Such lithiated materials, however, not only are the manufacturing/processing costs high, but also the disposal costs after the end of their useful life are high, which can have a significant impact on the environment if not handled properly, and also present a potential safety hazard that is increasingly difficult to meet the needs of development.
In recent years, many new structural materials have been introduced to replace the conventional positive electrode materials, such as silicate, borate, olivine structural derivatives, and the like. However, the newly developed cathode material cannot meet the requirements of reversible lithium removal and lithium insertion, and is high in cost and not environment-friendly.
In view of the above, it is necessary to provide a technical solution to the above problems.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the invention provides a double-graphite-electrode battery to solve the problems of environmental unfriendliness and high cost of the existing anode material.
In order to achieve the purpose, the invention adopts the following technical scheme: a double-graphite electrode battery comprises a positive plate, a negative plate, electrolyte and a diaphragm which is arranged between the positive plate and the negative plate at intervals, wherein a positive active material of the positive plate is graphite or amorphous carbon-coated graphite; the negative active material of the negative plate is graphite or amorphous carbon-coated graphite; the working voltage of the battery is 4.5-5.5V.
The traditional positive electrode material containing transition metal is improved, replaced by graphite substances capable of being embedded with electrolyte salt anions and matched with a graphite negative electrode to form the graphite-graphite battery, so that the traditional concept is changed, and the full-graphite battery is realized. The graphite battery needs to work under high voltage, ClO4 -、BF4 -、PF6 -And (CF)3SO2)2N-The negative ions of the electrolyte salt are embedded into the graphite positive electrode, so that the number of the positive ions in the electrolyte is larger than that of the negative ions, namely the number of the lithium ions is excessive, the lithium ions are promoted to be embedded into the graphite negative electrode, and a loop is formed to obtain a complete battery. If the battery is operated at a voltage lower than 4.5V, the graphite positive electrode cannot be embedded, and the battery cannot be cycled. The positive electrode and the negative electrode are made of graphite as active materials, so that the cost of the lithium ion battery is reduced, the lithium ion battery does not contain transition metal elements, is environment-friendly, and meets the use requirements in the fields of solar energy, wind energy, tidal energy and the like.
Preferably, the electrolyte comprises lithium salt, fluorine-containing additive and solvent. Because the double-graphite battery needs to work under high voltage, the conventional electrolyte can only meet the use requirement of the double-graphite battery, a high-voltage electrolyte is newly developed, the electrolyte comprises a fluorine-containing additive, fluorine atoms in the additive are beneficial to the electrolyte to infiltrate an electrode and a diaphragm, and the intercalation rate of lithium ions is improved.
Preferably, the solvent comprises fluoroethylene carbonate and methyl ethyl carbonate, and the mass ratio of the fluoroethylene carbonate to the methyl ethyl carbonate is 2: 8-7: 3. FluorineThe ethylene carbonate is added into the electrolyte as a solvent, so that the dissolution of lithium salt can be promoted, and the hydrolysis of the lithium salt is inhibited compared with the traditional carbonate electrolyte. Through a large number of experiments, the inventor discovers that PF can be supported by controlling the mass ratio of fluoroethylene carbonate to methyl ethyl carbonate to be 2: 8-7: 3 and then performing synergistic action with a fluorine-containing additive6 -The lithium ion battery is embedded into the positive electrode graphite at a voltage of 4.5-5.5V, and meanwhile, a good SEI film can be formed on the surface of the negative electrode graphite, so that the lithium ion battery is supported to be embedded into the negative electrode graphite at 0.2V. A double graphite battery with good cycle performance is formed.
Preferably, the mass ratio of the fluoroethylene carbonate to the methyl ethyl carbonate is 3: 7-6: 4. More preferably, the mass ratio of fluoroethylene carbonate to ethyl methyl carbonate is 4: 6.
Preferably, the fluorine-containing additive comprises one or more of hexafluoroisopropanol, tetrafluoropropanol, hexafluorobutanol and octafluoropentanol. The fluorine-containing additive not only contains a plurality of fluorine atoms and is beneficial to infiltrating electrodes and diaphragms, but also can be used as a solvent to promote the dissolution of lithium salt, improve the conductivity of electrolyte and be more beneficial to the intercalation of lithium ions into negative electrode graphite. More preferably, hexafluoroisopropanol is preferably used as the fluorine-containing additive, and hexafluoroisopropanol as a highly polar solvent dissolves most of the substances, and exhibits excellent performance as an additive in the present invention.
The concentration of the fluorine-containing additive is 2-10 mmol/L. By controlling the mass ratio of the fluorine-containing additive to the fluoroethylene carbonate to the methyl ethyl carbonate, the cycle efficiency of the double-graphite battery can reach 90-97%.
Preferably, the concentration of the fluorine-containing additive is 4-7 mmol/L. More preferably, the fluorine-containing additive has a concentration of 5 mmol/L. Particularly, when the mass ratio of fluoroethylene carbonate to ethyl methyl carbonate is 4:6 and the concentration of the fluorine-containing additive is 5mmol/L, the cycle efficiency of the double graphite battery reaches 97%.
Preferably, the lithium salt is at least one of lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (fluorosulfonato) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium difluoro-phosphate, lithium tetrafluorooxalato-phosphate and lithium tetrafluoroborate.
Preferably, the electrolyte may further include other additives, such as one or more of vinylene carbonate, lithium difluorophosphate, vinyl sulfate, 1, 3-propane sultone, tris (trimethylsilyl) borate, tris (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphite, and vinyl ethylene carbonate.
Preferably, the working voltage of the battery is 4.8-5.2V, and more preferably 5.0V.
The invention has the beneficial effects that:
1) the invention relates to a double-graphite electrode battery, which comprises a positive plate, a negative plate, electrolyte and a diaphragm which is arranged between the positive plate and the negative plate at intervals, wherein a positive active material of the positive plate is graphite or amorphous carbon-coated graphite; the negative active material of the negative plate is graphite or amorphous carbon-coated graphite; the working voltage of the battery is 4.5-5.5V. Compared with the prior art, the anode and the cathode of the invention both adopt graphite as active materials, particularly, the graphite capable of being embedded with electrolyte salt anions replaces the traditional anode material, and the electrolyte salt anions such as ClO under high voltage are utilized4 -、BF4 -、PF6 -And (CF)3SO2)2N-Can be inserted into the graphite anode, and lithium ions are inserted into the graphite cathode to form a loop, thus obtaining a complete double-graphite battery. The battery does not contain transition metal elements, is environment-friendly, can meet the use requirements in the fields of solar energy, wind energy, tidal energy and the like, and effectively reduces the manufacturing cost of the battery by adopting graphite as an active material.
2) The double-graphite battery adopts high-pressure resistant electrolyte, the fluorine-containing additive and the solvent matrix consisting of fluoroethylene carbonate and methyl ethyl carbonate are added, the electrolyte can support the simultaneous embedding of a graphite anode and a graphite cathode through the synergistic effect, and the cycle efficiency can reach 97%.
3) The electrolyte used in the invention is suitable for working under high voltage, and provides possibility for large-scale commercial application of a high-voltage anode.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantageous effects will be described in further detail below with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
The negative plate uses graphite as a negative active substance, uses deionized water as a solvent of negative slurry, mixes and stirs 98% of the negative active substance, 1.0% of sodium carboxymethyl cellulose and 1.0% of styrene butadiene rubber to form negative slurry, coats, rolls, and cuts to obtain the negative plate.
The positive plate uses graphite as a negative active material, uses deionized water as a solvent of positive slurry, mixes and stirs 98% of the positive active material, 1.0% of sodium carboxymethyl cellulose and 1.0% of styrene butadiene rubber to form negative slurry, coats, rolls and cuts to obtain the positive plate.
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, ethylene carbonate and methyl ethyl carbonate are uniformly mixed according to the mass ratio of 30:70, the concentration is added into the mixed solution, and LiPF with the mass fraction of 16% is slowly added6Then, the mixture was stirred until it was completely dissolved, thereby obtaining an electrolytic solution of example 1. The electrolyte is a conventional electrolyte and is not described in more detail here.
Polyethylene (PE) is used as a base film, and a nano aluminum oxide coating is coated on the base film to be used as an isolating film.
And sequentially laminating the positive plate, the isolating film and the negative plate, winding the positive plate, the isolating film and the negative plate along the same direction to obtain a bare cell, packaging the bare cell by adopting an aluminum plastic film, and carrying out processes of packaging, shelving, formation, aging, secondary packaging, capacity grading and the like on the battery after liquid injection to obtain the double-graphite-electrode battery, wherein the working voltage of the double-graphite-electrode battery is 5.0V.
Example 2
The negative plate uses graphite as a negative active substance, uses deionized water as a solvent of negative slurry, mixes and stirs 98% of the negative active substance, 1.0% of sodium carboxymethyl cellulose and 1.0% of styrene butadiene rubber to form negative slurry, coats, rolls, and cuts to obtain the negative plate.
The positive plate uses graphite as a negative active material, uses deionized water as a solvent of positive slurry, mixes and stirs 98% of the positive active material, 1.0% of sodium carboxymethyl cellulose and 1.0% of styrene butadiene rubber to form negative slurry, coats, rolls and cuts to obtain the positive plate.
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, fluoroethylene carbonate, methyl ethyl carbonate, propylene carbonate and ethyl propionate are uniformly mixed according to the mass ratio of 40:60, hexafluoroisopropanol with the concentration of 5mmol/L is added into the mixed solution, and LiPF with the mass fraction of 16% is slowly added6Then, the mixture was stirred until it was completely dissolved, thereby obtaining an electrolytic solution of example 1.
Polyethylene (PE) is used as a base film, and a nano aluminum oxide coating is coated on the base film to be used as an isolating film.
And sequentially laminating the positive plate, the isolating film and the negative plate, winding the positive plate, the isolating film and the negative plate along the same direction to obtain a bare cell, packaging the bare cell by adopting an aluminum plastic film, and carrying out processes of packaging, shelving, formation, aging, secondary packaging, capacity grading and the like on the battery after liquid injection to obtain the double-graphite-electrode battery, wherein the working voltage of the double-graphite-electrode battery is 5V.
Example 3
The difference from example 2 is the preparation of the electrolyte.
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, fluoroethylene carbonate, methyl ethyl carbonate, propylene carbonate and ethyl propionate are uniformly mixed according to the mass ratio of 40:60, hexafluoroisopropanol with the concentration of 2mmol/L is added into the mixed solution, and LiPF with the mass fraction of 16% is slowly added6And stirred until it was completely dissolved, to obtain an electrolytic solution of example 3.
The rest is the same as embodiment 2, and the description is omitted here.
Example 4
The difference from example 2 is the preparation of the electrolyte.
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, fluoroethylene carbonate, methyl ethyl carbonate, propylene carbonate and ethyl propionate are uniformly mixed according to the mass ratio of 40:60, hexafluoroisopropanol with the concentration of 7mmol/L is added into the mixed solution, and LiPF with the mass fraction of 16% is slowly added6And stirred until it was completely dissolved, to obtain an electrolytic solution of example 4.
The rest is the same as embodiment 2, and the description is omitted here.
Example 5
The difference from example 2 is the preparation of the electrolyte.
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, fluoroethylene carbonate, methyl ethyl carbonate, propylene carbonate and ethyl propionate are uniformly mixed according to the mass ratio of 40:60, hexafluoroisopropanol with the concentration of 10mmol/L is added into the mixed solution, and LiPF with the mass fraction of 16% is slowly added6And stirred until it was completely dissolved, to obtain an electrolytic solution of example 5.
The rest is the same as embodiment 2, and the description is omitted here.
Example 6
The difference from example 2 is the preparation of the electrolyte.
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, fluoroethylene carbonate, methyl ethyl carbonate, propylene carbonate and ethyl propionate are uniformly mixed according to the mass ratio of 20:80, hexafluoroisopropanol with the concentration of 5mmol/L is added into the mixed solution, and LiPF with the mass fraction of 16% is slowly added6And stirred until it was completely dissolved, to obtain an electrolytic solution of example 6.
The rest is the same as embodiment 2, and the description is omitted here.
Example 7
The difference from example 2 is the preparation of the electrolyte.
Fluoroethylene carbonate, ethyl methyl carbonate, propylene carbonate and ethyl propionate were mixed at a mass ratio of 50:50 in an argon-filled glove box (moisture < 10ppm, oxygen < 1ppm)Uniformly mixing, adding hexafluoroisopropanol with the concentration of 5mmol/L into the mixed solution, and slowly adding LiPF with the mass fraction of 16%6And stirred until it was completely dissolved, to obtain an electrolytic solution of example 7.
The rest is the same as embodiment 2, and the description is omitted here.
Example 8
The difference from example 2 is the preparation of the electrolyte.
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, fluoroethylene carbonate, methyl ethyl carbonate, propylene carbonate and ethyl propionate are uniformly mixed according to the mass ratio of 70:30, hexafluoroisopropanol with the concentration of 5mmol/L is added into the mixed solution, and LiPF with the mass fraction of 16% is slowly added6And stirred until it was completely dissolved, to obtain an electrolytic solution of example 8.
The rest is the same as embodiment 2, and the description is omitted here.
Example 9
The difference from example 2 is the preparation of the electrolyte.
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, fluoroethylene carbonate, methyl ethyl carbonate, propylene carbonate and ethyl propionate are uniformly mixed according to the mass ratio of 40:60, tetrafluoropropanol with the concentration of 5mmol/L is added into the mixed solution, and LiPF with the mass fraction of 16% is slowly added6And stirred until it was completely dissolved, to obtain an electrolytic solution of example 9.
The rest is the same as embodiment 2, and the description is omitted here.
Example 10
The difference from example 2 is the preparation of the electrolyte.
In a glove box (moisture is less than 10ppm, oxygen content is less than 1ppm) filled with argon, fluoroethylene carbonate, methyl ethyl carbonate, propylene carbonate and ethyl propionate are uniformly mixed according to the mass ratio of 40:60, hexafluorobutanol with the concentration of 5mmol/L is added into the mixed solution, and LiPF with the mass fraction of 16% is slowly added6Then, the mixture was stirred until it was completely dissolved, thereby obtaining an electrolytic solution of example 10.
The rest is the same as embodiment 2, and the description is omitted here.
Example 11
The difference from example 2 is the operating voltage of the double graphite electrode cell.
And sequentially laminating the positive plate, the isolating film and the negative plate, winding the positive plate, the isolating film and the negative plate along the same direction to obtain a bare cell, packaging the bare cell by adopting an aluminum plastic film, and carrying out processes of packaging, shelving, formation, aging, secondary packaging, capacity grading and the like on the battery after liquid injection to obtain the double-graphite-electrode battery, wherein the working voltage of the double-graphite-electrode battery is 4.5V.
The rest is the same as embodiment 2, and the description is omitted here.
Example 12
The difference from example 2 is the operating voltage of the double graphite electrode cell.
And sequentially laminating the positive plate, the isolating film and the negative plate, winding the positive plate, the isolating film and the negative plate along the same direction to obtain a bare cell, packaging the bare cell by adopting an aluminum plastic film, and carrying out processes of packaging, shelving, formation, aging, secondary packaging, capacity grading and the like on the battery after liquid injection to obtain the double-graphite-electrode battery, wherein the working voltage of the double-graphite-electrode battery is 4.8V.
The rest is the same as embodiment 2, and the description is omitted here.
Example 13
The difference from example 2 is the operating voltage of the double graphite electrode cell.
And sequentially laminating the positive plate, the isolating film and the negative plate, winding the positive plate, the isolating film and the negative plate along the same direction to obtain a bare cell, packaging the bare cell by adopting an aluminum plastic film, and carrying out processes of packaging, shelving, formation, aging, secondary packaging, capacity grading and the like on the battery after liquid injection to obtain the double-graphite-electrode battery, wherein the working voltage of the double-graphite-electrode battery is 5.5V.
The rest is the same as embodiment 2, and the description is omitted here.
Example 14
The difference from example 6 is the operating voltage of the double graphite electrode cell.
And sequentially laminating the positive plate, the isolating film and the negative plate, winding the positive plate, the isolating film and the negative plate along the same direction to obtain a bare cell, packaging the bare cell by adopting an aluminum plastic film, and carrying out processes of packaging, shelving, formation, aging, secondary packaging, capacity grading and the like on the battery after liquid injection to obtain the double-graphite-electrode battery, wherein the working voltage of the double-graphite-electrode battery is 5.2V.
The rest is the same as embodiment 6, and the description is omitted here.
Example 15
The difference from example 7 is the operating voltage of the double graphite electrode cell.
And sequentially laminating the positive plate, the isolating film and the negative plate, winding the positive plate, the isolating film and the negative plate along the same direction to obtain a bare cell, packaging the bare cell by adopting an aluminum plastic film, and carrying out processes of packaging, shelving, formation, aging, secondary packaging, capacity grading and the like on the battery after liquid injection to obtain the double-graphite-electrode battery, wherein the working voltage of the double-graphite-electrode battery is 5.2V.
The rest is the same as embodiment 7, and the description is omitted here.
Comparative example 1
The difference from example 1 is the operating voltage of the double graphite electrode cell.
And sequentially laminating the positive plate, the isolating film and the negative plate, winding the positive plate, the isolating film and the negative plate along the same direction to obtain a bare cell, packaging the bare cell by adopting an aluminum plastic film, and carrying out processes of packaging, shelving, formation, aging, secondary packaging, capacity grading and the like on the battery after liquid injection to obtain the double-graphite-electrode battery, wherein the working voltage of the double-graphite-electrode battery is 4.2V.
The rest of the process is the same as example 1, and the description is omitted here
The capacity retention rate and the charge-discharge efficiency of the same batch of the double-graphite-electrode batteries prepared in examples 1 to 15 and comparative example 1 were tested.
The test results are shown in Table 1.
TABLE 1 Dual graphite electrode Battery Performance test results
Figure BDA0002199359570000091
Figure BDA0002199359570000101
As can be seen from comparative example 1, when the operating voltage of the double graphite electrode battery was maintained at 4.2V, which is the operating voltage of the conventional lithium battery, the circulation of lithium ions inside the double graphite battery could not be achieved, and thus, conventionally, it was considered that the double graphite battery could not be achieved. However, the inventor of the present invention finds that, by increasing the voltage, when the operating voltage is 4.5V or more, the circulation of lithium ions in the double graphite battery can be achieved, but the test result of example 1 also finds that the conventional electrolyte cannot adapt to the operation under high voltage, and even if the circulation of the double graphite battery can be achieved, the capacity retention ratio of 500 cycles of normal temperature circulation, the capacity retention ratio of 300 cycles of 55-1C/1C circulation, and the charge-discharge efficiency are too low, and therefore, the double graphite battery cannot adapt to industrial production and application.
The inventor obtains an electrolyte capable of adapting to lithium ion circulation in a double-graphite-electrode battery through a large number of research experiments, and the test results of the embodiments 2 to 15 can obviously show that the electrolyte can be applied to lithium ion circulation in the double-graphite-electrode battery. Compared with the embodiment 1, namely the double-graphite battery obtained by the conventional electrolyte, the capacity retention rate of the double-graphite battery obtained by improving the electrolyte after the electrolyte is cycled at normal temperature for 500 weeks, the capacity retention rate of the double-graphite battery obtained by cycling at 55-1C/1C for 300 weeks and the charge-discharge efficiency are greatly improved. From examples 2 to 5, it can be found that when the concentration of the hexafluoroisopropanol added as an additive is 5mmol/L, the retention rate of the cycle capacity of the double graphite battery is maximized, the charge-discharge efficiency also reaches 97%, and the cycle efficiency tends to decrease with the increase of the concentration of the hexafluoroisopropanol, presumably because the density of fluorine atoms is too high to prevent the intercalation of lithium ions, and a proper amount of fluorine atoms is more beneficial to the wetting electrode and the separator, and the hexafluoroisopropanol itself can be used as a high-polarity solvent to promote the dissolution of lithium salts, so that the intercalation of lithium ions into negative electrode graphite is improved.
It is also understood from examples 2 and 11 to 12 that the cycle capacity retention ratio and the charge/discharge efficiency both increase with an increase in the operating voltage, but the performance of the double graphite battery tends to decrease when the operating voltage increases to 5.5V, presumably because the electrolyte cannot be operated at such a high voltage. From comparison of examples 6 and 14 and examples 7 and 15, it can be seen that when the operating voltage is 5.0 to 5.2V,the performance of the double-graphite electrode battery is comparable, and the battery performance is better when the voltage is 5.0V on the whole. The main reason is that under the high voltage of 5.0-5.2V, the electrolyte not only supports PF6 -The lithium ion battery can be embedded into the positive electrode graphite, and a better SEI film can be formed on the surface of the negative electrode graphite to support the lithium ion to be embedded into the negative electrode graphite.
As can be seen from the above analysis, the positive and negative electrodes of the present invention all use graphite as the active material, and particularly, graphite capable of intercalating electrolyte salt anions such as ClO is used to replace the conventional positive electrode material, and the electrolyte salt anions such as ClO are used under high voltage4 -、BF4 -、PF6 -And (CF)3SO2)2N-Can be inserted into the graphite anode, and lithium ions are inserted into the graphite cathode to form a loop, thus obtaining a complete double-graphite battery. The battery does not contain transition metal elements, is environment-friendly, can meet the use requirements in the fields of solar energy, wind energy, tidal energy and the like, and effectively reduces the manufacturing cost of the battery by adopting graphite as an active material.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (9)

1. The utility model provides a two graphite electrode batteries, includes positive plate, negative pole piece, electrolyte and interval in positive plate with diaphragm between the negative pole piece, its characterized in that:
the positive active material of the positive plate is graphite or amorphous carbon-coated graphite;
the negative active material of the negative plate is graphite or amorphous carbon-coated graphite;
the working voltage of the battery is 4.5-5.5V.
2. The battery of claim 1, wherein the electrolyte comprises a lithium salt, a fluorine-containing additive, and a solvent.
3. The battery as claimed in claim 2, wherein the solvent comprises fluoroethylene carbonate and ethyl methyl carbonate, and the mass ratio of fluoroethylene carbonate to ethyl methyl carbonate is 2: 8-7: 3.
4. The battery with double graphite electrodes as claimed in claim 2, wherein the mass ratio of fluoroethylene carbonate to ethyl methyl carbonate is 3: 7-6: 4.
5. The battery of claim 2, wherein the fluorine-containing additive is one or more of hexafluoroisopropanol, tetrafluoropropanol, hexafluorobutanol, and octafluoropentanol.
6. The battery of claim 2, wherein the fluorine-containing additive is present in a concentration of 2 to 10 mmol/L.
7. The battery of claim 6, wherein the fluorine-containing additive is present in a concentration of 4 to 7 mmol/L.
8. The battery of claim 2, wherein the lithium salt is at least one of lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (fluorosulfonato) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium difluoro (oxalato) phosphate, lithium tetrafluoro (oxalato) phosphate, and lithium tetrafluoroborate.
9. The battery of claim 1, wherein the operating voltage of the battery is 4.8-5.2V.
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