CN114142080B - Super-capacity graphene battery and preparation method thereof - Google Patents
Super-capacity graphene battery and preparation method thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 115
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 104
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 44
- -1 fullerene compound Chemical class 0.000 claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 36
- 239000002096 quantum dot Substances 0.000 claims abstract description 34
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 34
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 23
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 22
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 17
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000007773 negative electrode material Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 19
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 12
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims 2
- 239000012043 crude product Substances 0.000 claims 2
- 238000010992 reflux Methods 0.000 claims 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims 2
- 239000004327 boric acid Substances 0.000 claims 1
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims 1
- 239000005051 trimethylchlorosilane Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 238000000034 method Methods 0.000 description 39
- 239000011248 coating agent Substances 0.000 description 31
- 238000000576 coating method Methods 0.000 description 31
- 239000007788 liquid Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000002033 PVDF binder Substances 0.000 description 17
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000006258 conductive agent Substances 0.000 description 12
- 238000001125 extrusion Methods 0.000 description 12
- 238000005096 rolling process Methods 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 238000005056 compaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000009998 heat setting Methods 0.000 description 6
- 238000009775 high-speed stirring Methods 0.000 description 6
- 235000011837 pasties Nutrition 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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 discloses a super-capacity graphene battery, which is characterized in that the positive electrode material of the lithium metal graphene battery is a nitrogen-doped nickel-cobalt-manganese-graphene-based compound; the negative electrode material of the lithium metal graphene battery is a titanium dioxide quantum dot/metal lithium/fullerene compound; the diaphragm of the lithium metal graphene battery is prepared from the following components in parts by weight: 50-60 parts of hyperbranched polyborosiloxane containing epoxy groups, 10-15 parts of melamine and 8-10 parts of nano calcium carbonate. The invention also provides a preparation method of the lithium metal graphene battery. The lithium metal graphene battery disclosed by the invention has the advantages of high theoretical specific capacity, good electrochemical stability, high and low temperature resistance and excellent use safety.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a super-capacity graphene battery and a preparation method thereof.
Background
In recent years, with technological progress and increasing demand, lithium ion batteries are moving from electronic terminal devices to electric automobiles
And the energy storage technology field has become necessary. The lithium ion battery has the advantages of high energy density and voltage, long cycle life, low self-discharge rate, no memory effect, stable discharge voltage, quick charge and discharge, environmental protection and the like, and is a main choice of sustainable power batteries, and is known as an ideal power supply in the 21 st century.
The main constituent materials of the lithium ion battery comprise electrolyte, diaphragm materials, anode and cathode materials and the like. As a main body for storing lithium, the anode and cathode materials play an important role in the lithium ion battery, the capacity of the anode and cathode materials is one of important factors influencing the capacity of the battery, the quality of the performance of the anode and cathode materials directly influences the battery capacity and the cycle service life of the lithium ion battery, and the cost of the anode and cathode materials directly determines the cost of the battery. The current cathode materials of lithium ion batteries commercially applied to electric automobiles mainly comprise lithium iron phosphate, lithium manganate and ternary materials containing nickel cobalt lithium manganate and nickel cobalt lithium aluminate. However, these existing positive electrode materials have more or less defects that the consistency and energy density are low, the cycle performance and electrochemical stability are poor, and the safety performance, the cycle performance, the low-temperature performance and other key technologies need to be further improved. The diaphragm material plays a double role in lithium ion transfer and positive and negative electrode electron conductivity blocking in the lithium battery. However, the traditional polyolefin diaphragm has a low melting point, and shrinkage can occur after heating, so that the contact short circuit of the anode and the cathode of the battery is caused; in addition, polyolefin separators themselves have poor wettability to the electrolyte and low liquid absorption, thereby affecting the cycle performance of the battery.
Chinese patent document CN 109037560B relates to a super-capacity graphene battery and a graphene battery. The positive electrode of the lithium metal graphene battery is a graphene electrode made of flaky graphene, the negative electrode of the lithium metal graphene battery is lithium metal, the electrolyte of the lithium metal graphene battery is an organic solvent system, the diaphragm of the lithium metal graphene battery is a high-strength thin-film polyolefin porous membrane, the dosage of the lithium metal is 1-2 times of the mass of the graphene electrode, and an organic electrolyte solution used in a loop forming process comprises an organic solvent and electrolyte salt. It has higher working voltage and specific energy, the open-circuit voltage is 2-4.2V, the specific energy can reach 200-600 W.h/kg and 500-1000 W.h/L; the battery can work within the range of-40 to +50 ℃, the storage life of the battery exceeds 10 years at normal temperature, no gas is separated out during the storage and discharge processes, and the safety performance is good. However, the cycle performance, electrochemical stability, and high and low temperature resistance of the battery are required to be further improved.
Therefore, how to provide a lithium ion battery with high theoretical specific capacity, good electrochemical stability, excellent high and low temperature resistance and excellent use safety is a difficult problem to be solved by researchers in the industry.
Disclosure of Invention
The invention mainly aims to provide a super-capacity graphene battery, which has high theoretical specific capacity, good electrochemical stability, high and low temperature resistance and excellent use safety. Meanwhile, the second aim of the invention is to provide a preparation method of the lithium metal graphene battery, which has simple process, small dependence on equipment and high preparation efficiency and is suitable for continuous production.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the super-capacity graphene battery is characterized in that a positive electrode material of the lithium metal graphene battery is a nitrogen-doped nickel-cobalt-manganese-graphene-based compound; the negative electrode material of the lithium metal graphene battery is a titanium dioxide quantum dot/metal lithium/fullerene compound; the diaphragm of the lithium metal graphene battery is prepared from the following components in parts by weight: 50-60 parts of hyperbranched polyborosiloxane containing epoxy groups, 10-15 parts of melamine and 8-10 parts of nano calcium carbonate.
Preferably, the nitrogen-doped nickel-cobalt-manganese-graphene-based compound is a mixture formed by uniformly mixing nitrogen-doped nickel-cobalt-manganese ternary materials and graphene according to a mass ratio of (3-5): 1.
Preferably, the ternary material of nickel cobalt manganese doped with nitrogen is prepared according to the method of example 1 in Chinese patent document CN 107565127B.
Preferably, the titanium dioxide quantum dot/metallic lithium/fullerene compound is a mixture formed by uniformly mixing titanium dioxide quantum dots, metallic lithium and fullerene according to the mass ratio of 1 (4-6) (0.3-0.6).
Preferably, the titanium dioxide quantum dot is prepared according to the method of example 1 in chinese patent document CN108906013 a.
Preferably, the electrolyte of the lithium metal graphene battery is a lithium hexafluorophosphate solution with the concentration of 0.8-1.2 mol/L.
Preferably, the solvent of the lithium hexafluorophosphate solution is a mixture formed by mixing ethylene carbonate and diethyl carbonate according to the mass ratio of 1 (3-5).
Preferably, the hyperbranched polyborosiloxane containing epoxy groups is prepared according to the method of example 1 in chinese patent document CN 107868252B.
Preferably, the particle size of the nano calcium carbonate is 200-500nm.
The second object of the present invention is to provide a method for preparing the lithium metal graphene battery, which is characterized by comprising the following steps:
step S1, uniformly mixing a titanium dioxide quantum dot/metallic lithium/fullerene compound, a conductive agent Super P and polyvinylidene fluoride PVDF according to a mass ratio of 8:1:1, then dripping N-methyl pyrrolidone into the mixture, uniformly stirring the mixture to form a viscous pasty viscous liquid, uniformly coating the viscous liquid on a copper foil through a coating machine, compacting the coated surface density of 160-260g/m 2 Compacting density of 2.0-2.8g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then continuously slitting and continuously rolling to obtain a positive pole piece;
step S2, uniformly mixing the titanium dioxide quantum dot/metallic lithium/fullerene compound, the conductive agent Super P and PVDF according to a mass ratio of 8:1:1, then dripping N-methyl pyrrolidone into the mixture, uniformly stirring the mixture into thick uniform stable slurry by using double-planetary vacuum high-speed stirring equipment, and then stably and uniformly coating the prepared slurry on the surface of a copper foil by using an extrusion type double-sided coating machine, wherein the coating surface density is 150-220g/m 2 Compaction density of 1.5-1.8g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then continuously slitting and continuously rolling to obtain a negative electrode plate;
step S3, uniformly mixing hyperbranched polyborosiloxane containing epoxy groups, melamine and nano calcium carbonate according to the weight ratio, carrying out melt extrusion and heat setting, then placing in a hydrochloric acid solution with the mass percentage concentration of 9-12% for soaking for 3-6 hours, taking out, washing with water for 3-6 times, and finally placing in a vacuum drying oven for drying to constant weight at 90-95 ℃ to finally obtain the diaphragm;
and S4, assembling and injecting liquid to obtain the lithium metal graphene battery.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) The preparation method of the lithium metal graphene battery provided by the invention adopts a conventional process route and production equipment, has low capital investment, does not need to modify the original production line, has high preparation efficiency, and is suitable for continuous production;
(2) According to the lithium metal graphene battery provided by the invention, the nitrogen-doped nickel-cobalt-manganese-graphene-based compound is used as the positive electrode material, the advantages of nitrogen-doped nickel-cobalt-manganese and graphene are combined, and the advantages of nitrogen-doped nickel-cobalt-manganese and graphene are mutually matched, so that the stability of the lithium metal graphene battery can be ensured under the combined action, the chargeability of the lithium metal graphene battery can be improved, and the lithium metal graphene battery is excellent in electrochemical performance, safety performance, cycle performance and low temperature resistance;
(3) According to the lithium metal graphene battery provided by the invention, the negative electrode material of the lithium metal graphene battery is the titanium dioxide quantum dot/metal lithium/fullerene compound, and through mutual cooperation and combined action of the components, the conductivity can be improved, so that the transmission and electron migration of lithium ions in the charge and discharge process are enhanced, and the capacity retention rate, multiplying power, circulation and other electrochemical performances of the material are obviously improved; the reversibility in the electrochemical process can be improved, and the volume expansion problem generated in the lithium intercalation and deintercalation process can be effectively solved;
(4) The invention provides a lithium metal graphene battery, wherein a diaphragm of the lithium metal graphene battery is prepared from the following components in parts by weight: 50-60 parts of hyperbranched polyborosiloxane containing epoxy groups, 10-15 parts of melamine and 8-10 parts of nano calcium carbonate; the hyperbranched polyborosiloxane containing epoxy groups can perform epoxy ring-opening reaction with amino groups on melamine to form a three-dimensional network structure, so that the comprehensive performance of the film is effectively improved; the formed film material has high melting point and good thermal stability, and the hydrophilic groups such as hydroxyl formed by epoxy ring-opening reaction can improve the wettability of the diaphragm to electrolyte, thereby being beneficial to the prevention of a battery and effectively prolonging the service life of the battery;
(5) According to the lithium metal graphene battery provided by the invention, through the cooperation of the battery anode material, the battery cathode material, the diaphragm and the electrolyte, interaction is mutually influenced, so that the prepared lithium metal graphene battery has high theoretical specific capacity, good electrochemical stability, high and low temperature resistance and excellent use safety.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
The super-capacity graphene battery is characterized in that a positive electrode material of the lithium metal graphene battery is a nitrogen-doped nickel-cobalt-manganese-graphene-based compound; the negative electrode material of the lithium metal graphene battery is a titanium dioxide quantum dot/metal lithium/fullerene compound; the diaphragm of the lithium metal graphene battery is prepared from the following components in parts by weight: 50 parts of hyperbranched polyborosiloxane containing epoxy groups, 10 parts of melamine and 8 parts of nano calcium carbonate.
The nitrogen-doped nickel-cobalt-manganese-graphene-based composite is a mixture formed by uniformly mixing nitrogen-doped nickel-cobalt-manganese ternary materials and graphene according to a mass ratio of 3:1; the nitrogen-doped nickel-cobalt-manganese ternary material is prepared according to the method of example 1 in Chinese patent document CN 107565127B.
The titanium dioxide quantum dot/metallic lithium/fullerene compound is a mixture formed by uniformly mixing titanium dioxide quantum dots, metallic lithium and fullerene according to a mass ratio of 1:4:0.3; the titanium dioxide quantum dot is prepared according to the method of example 1 in Chinese patent document CN 108906013A.
The electrolyte of the lithium metal graphene battery is a lithium hexafluorophosphate solution with the concentration of 0.8 mol/L; the solvent of the lithium hexafluorophosphate solution is a mixture formed by mixing ethylene carbonate and diethyl carbonate according to a mass ratio of 1:3; the hyperbranched polyborosiloxane containing epoxy groups is prepared according to the method of example 1 in Chinese patent document CN 107868252B; the particle size of the nano calcium carbonate is 200nm.
The preparation method of the lithium metal graphene battery is characterized by comprising the following steps of:
step S1, uniformly mixing a titanium dioxide quantum dot/metallic lithium/fullerene compound, a conductive agent Super P and polyvinylidene fluoride PVDF according to a mass ratio of 8:1:1, then dripping N-methyl pyrrolidone into the mixture, uniformly stirring the mixture to form a viscous pasty viscous liquid, uniformly coating the viscous liquid on a copper foil through a coating machine, compacting the coated surface density of 160g/m 2 Compaction density of 2.0g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then continuously slitting and continuously rolling to obtain a positive pole piece;
step S2, uniformly mixing the titanium dioxide quantum dot/metallic lithium/fullerene compound, the conductive agent Super P and PVDF according to a mass ratio of 8:1:1, then dripping N-methyl pyrrolidone into the mixture, uniformly stirring the mixture into thick uniform stable slurry by using double-planetary vacuum high-speed stirring equipment, and then stably and uniformly coating the prepared slurry on the surface of a copper foil by using an extrusion type double-sided coating machine, wherein the coating surface density is 150g/m 2 Compaction density of 1.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then continuously slitting and continuously rolling to obtain a negative electrode plate;
step S3, uniformly mixing hyperbranched polyborosiloxane containing epoxy groups, melamine and nano calcium carbonate according to the weight ratio, carrying out melt extrusion and heat setting, then placing in a hydrochloric acid solution with the mass percentage concentration of 9% for soaking for 3 hours, taking out, washing with water for 3 times, and finally placing in a vacuum drying oven for drying at 90 ℃ until the weight is constant, thus obtaining the diaphragm;
and S4, assembling and injecting liquid to obtain the lithium metal graphene battery.
Example 2
The super-capacity graphene battery is characterized in that a positive electrode material of the lithium metal graphene battery is a nitrogen-doped nickel-cobalt-manganese-graphene-based compound; the negative electrode material of the lithium metal graphene battery is a titanium dioxide quantum dot/metal lithium/fullerene compound; the diaphragm of the lithium metal graphene battery is prepared from the following components in parts by weight: 53 parts of hyperbranched polyborosiloxane containing epoxy groups, 11 parts of melamine and 8.5 parts of nano calcium carbonate.
The nitrogen-doped nickel-cobalt-manganese-graphene-based composite is a mixture formed by uniformly mixing nitrogen-doped nickel-cobalt-manganese ternary materials and graphene according to a mass ratio of 3.5:1; the nitrogen-doped nickel-cobalt-manganese ternary material is prepared according to the method of example 1 in Chinese patent document CN 107565127B.
The titanium dioxide quantum dot/metallic lithium/fullerene compound is a mixture formed by uniformly mixing titanium dioxide quantum dots, metallic lithium and fullerene according to the mass ratio of 1:4.5:0.4; the titanium dioxide quantum dot is prepared according to the method of example 1 in Chinese patent document CN 108906013A.
The electrolyte of the lithium metal graphene battery is a lithium hexafluorophosphate solution with the concentration of 0.9 mol/L; the solvent of the lithium hexafluorophosphate solution is a mixture formed by mixing ethylene carbonate and diethyl carbonate according to a mass ratio of 1:3.5.
The hyperbranched polyborosiloxane containing epoxy groups is prepared according to the method of example 1 in Chinese patent document CN 107868252B; the particle size of the nano calcium carbonate is 300nm.
The preparation method of the lithium metal graphene battery is characterized by comprising the following steps of:
step S1, uniformly mixing a titanium dioxide quantum dot/metallic lithium/fullerene compound, a conductive agent Super P and polyvinylidene fluoride PVDF according to a mass ratio of 8:1:1, then dripping N-methyl pyrrolidone into the mixture, uniformly stirring the mixture to form a viscous pasty viscous liquid, uniformly coating the viscous liquid on a copper foil through a coating machine, compacting the coated surface density of 180g/m 2 Compact density 2.2g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then continuously slitting and continuously rolling to obtain a positive pole piece;
step S2, uniformly mixing the titanium dioxide quantum dot/metallic lithium/fullerene compound, the conductive agent Super P and PVDF according to a mass ratio of 8:1:1, then dripping N-methyl pyrrolidone into the mixture, uniformly stirring the mixture into thick uniform stable slurry by using double-planetary vacuum high-speed stirring equipment, and then stably and uniformly coating the prepared slurry on the surface of a copper foil by using an extrusion type double-sided coating machine, wherein the coating surface density is 170g/m 2 Compaction density of 1.6g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then continuously slitting and continuously rolling to obtain a negative electrode plate;
step S3, uniformly mixing hyperbranched polyborosiloxane containing epoxy groups, melamine and nano calcium carbonate according to the weight ratio, carrying out melt extrusion and heat setting, then placing in a hydrochloric acid solution with the mass percentage concentration of 10% for soaking for 4 hours, taking out, washing with water for 4 times, and finally placing in a vacuum drying oven at 92 ℃ for drying to constant weight, thus obtaining the diaphragm;
and S4, assembling and injecting liquid to obtain the lithium metal graphene battery.
Example 3
The super-capacity graphene battery is characterized in that a positive electrode material of the lithium metal graphene battery is a nitrogen-doped nickel-cobalt-manganese-graphene-based compound; the negative electrode material of the lithium metal graphene battery is a titanium dioxide quantum dot/metal lithium/fullerene compound; the diaphragm of the lithium metal graphene battery is prepared from the following components in parts by weight: 55 parts of hyperbranched polyborosiloxane containing epoxy groups, 13 parts of melamine and 9 parts of nano calcium carbonate.
The nitrogen-doped nickel-cobalt-manganese-graphene-based composite is a mixture formed by uniformly mixing nitrogen-doped nickel-cobalt-manganese ternary materials and graphene according to a mass ratio of 4:1; the nitrogen-doped nickel-cobalt-manganese ternary material is prepared according to the method of example 1 in Chinese patent document CN 107565127B.
The titanium dioxide quantum dot/metallic lithium/fullerene compound is a mixture formed by uniformly mixing titanium dioxide quantum dots, metallic lithium and fullerene according to a mass ratio of 1:5:0.45; the titanium dioxide quantum dot is prepared according to the method of example 1 in Chinese patent document CN 108906013A.
The electrolyte of the lithium metal graphene battery is lithium hexafluorophosphate solution with the concentration of 1 mol/L; the solvent of the lithium hexafluorophosphate solution is a mixture formed by mixing ethylene carbonate and diethyl carbonate according to a mass ratio of 1:4; the hyperbranched polyborosiloxane containing epoxy groups is prepared according to the method of example 1 in Chinese patent document CN 107868252B; the particle size of the nano calcium carbonate is 350nm.
The preparation method of the lithium metal graphene battery is characterized by comprising the following steps of:
step S1, titanium dioxide quantum dot/metallic lithium/fullerene compound, conductive agent Super P and polyUniformly mixing vinylidene fluoride PVDF according to a mass ratio of 8:1:1, then dripping N-methyl pyrrolidone into the mixture, uniformly stirring the mixture to form a thick pasty viscous liquid, uniformly coating the viscous liquid on a copper foil by a coating machine, compacting the copper foil, and coating the copper foil with a surface density of 210g/m 2 Compact density 2.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then continuously slitting and continuously rolling to obtain a positive pole piece;
step S2, uniformly mixing the titanium dioxide quantum dot/metallic lithium/fullerene compound, the conductive agent Super P and PVDF according to a mass ratio of 8:1:1, then dripping N-methyl pyrrolidone into the mixture, uniformly stirring the mixture into thick uniform stable slurry by using double-planetary vacuum high-speed stirring equipment, and then stably and uniformly coating the prepared slurry on the surface of a copper foil by using an extrusion type double-sided coating machine, wherein the coating surface density is 190g/m 2 Compaction density of 1.65g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then continuously slitting and continuously rolling to obtain a negative electrode plate;
step S3, uniformly mixing hyperbranched polyborosiloxane containing epoxy groups, melamine and nano calcium carbonate according to the weight ratio, carrying out melt extrusion and heat setting, then placing in a hydrochloric acid solution with the mass percentage concentration of 10.5% for soaking for 5 hours, taking out, washing with water for 5 times, and finally placing in a vacuum drying oven for drying at 93 ℃ until the weight is constant, thus finally obtaining the diaphragm;
and S4, assembling and injecting liquid to obtain the lithium metal graphene battery.
Example 4
The super-capacity graphene battery is characterized in that a positive electrode material of the lithium metal graphene battery is a nitrogen-doped nickel-cobalt-manganese-graphene-based compound; the negative electrode material of the lithium metal graphene battery is a titanium dioxide quantum dot/metal lithium/fullerene compound; the diaphragm of the lithium metal graphene battery is prepared from the following components in parts by weight: 58 parts of hyperbranched polyborosiloxane containing epoxy groups, 14 parts of melamine and 9.5 parts of nano calcium carbonate.
The nitrogen-doped nickel-cobalt-manganese-graphene-based composite is a mixture formed by uniformly mixing nitrogen-doped nickel-cobalt-manganese ternary materials and graphene according to a mass ratio of 4.5:1; the nitrogen-doped nickel-cobalt-manganese ternary material is prepared according to the method of example 1 in Chinese patent document CN 107565127B.
The titanium dioxide quantum dot/metallic lithium/fullerene compound is a mixture formed by uniformly mixing titanium dioxide quantum dots, metallic lithium and fullerene according to the mass ratio of 1:5.5:0.55; the titanium dioxide quantum dot is prepared according to the method of example 1 in Chinese patent document CN 108906013A; the electrolyte of the lithium metal graphene battery is lithium hexafluorophosphate solution with the concentration of 1.1 mol/L; the solvent of the lithium hexafluorophosphate solution is a mixture formed by mixing ethylene carbonate and diethyl carbonate according to a mass ratio of 1:4.5.
The hyperbranched polyborosiloxane containing epoxy groups is prepared according to the method of example 1 in Chinese patent document CN 107868252B; the particle size of the nano calcium carbonate is 450nm.
The preparation method of the lithium metal graphene battery is characterized by comprising the following steps of:
step S1, uniformly mixing a titanium dioxide quantum dot/metallic lithium/fullerene compound, a conductive agent Super P and polyvinylidene fluoride PVDF according to a mass ratio of 8:1:1, then dripping N-methyl pyrrolidone into the mixture, uniformly stirring the mixture to form a viscous pasty viscous liquid, uniformly coating the viscous liquid on a copper foil through a coating machine, compacting the coated surface density of 250g/m 2 Compact density 2.7g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then continuously slitting and continuously rolling to obtain a positive pole piece;
step S2, uniformly mixing the titanium dioxide quantum dot/metallic lithium/fullerene compound, the conductive agent Super P and PVDF according to a mass ratio of 8:1:1, then dripping N-methyl pyrrolidone into the mixture, uniformly stirring the mixture into thick uniform stable slurry by using double-planetary vacuum high-speed stirring equipment, and then stably and uniformly coating the prepared slurry on the surface of a copper foil by using an extrusion type double-sided coating machine, wherein the coating surface density is 210g/m 2 A compacted density of 1.75g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then continuously slitting and continuously rolling to obtain a negative electrode plate;
step S3, uniformly mixing hyperbranched polyborosiloxane containing epoxy groups, melamine and nano calcium carbonate according to the weight ratio, carrying out melt extrusion and heat setting, then placing in a hydrochloric acid solution with the mass percentage concentration of 11% for soaking for 5.5 hours, taking out, washing with water for 5 times, and finally placing in a vacuum drying oven for drying at 94 ℃ until the weight is constant, thus finally obtaining the diaphragm;
and S4, assembling and injecting liquid to obtain the lithium metal graphene battery.
Example 5
The super-capacity graphene battery is characterized in that a positive electrode material of the lithium metal graphene battery is a nitrogen-doped nickel-cobalt-manganese-graphene-based compound; the negative electrode material of the lithium metal graphene battery is a titanium dioxide quantum dot/metal lithium/fullerene compound; the diaphragm of the lithium metal graphene battery is prepared from the following components in parts by weight: 60 parts of hyperbranched polyborosiloxane containing epoxy groups, 15 parts of melamine and 10 parts of nano calcium carbonate.
The nitrogen-doped nickel-cobalt-manganese-graphene-based composite is a mixture formed by uniformly mixing nitrogen-doped nickel-cobalt-manganese ternary materials and graphene according to a mass ratio of 5:1; the nitrogen-doped nickel-cobalt-manganese ternary material is prepared according to the method of example 1 in Chinese patent document CN 107565127B.
The titanium dioxide quantum dot/metallic lithium/fullerene compound is a mixture formed by uniformly mixing titanium dioxide quantum dots, metallic lithium and fullerene according to a mass ratio of 1:6:0.6; the titanium dioxide quantum dot is prepared according to the method of example 1 in Chinese patent document CN 108906013A.
The electrolyte of the lithium metal graphene battery is lithium hexafluorophosphate solution with the concentration of 1.2 mol/L; the solvent of the lithium hexafluorophosphate solution is a mixture formed by mixing ethylene carbonate and diethyl carbonate according to a mass ratio of 1:5; the hyperbranched polyborosiloxane containing epoxy groups is prepared according to the method of example 1 in Chinese patent document CN 107868252B; the particle size of the nano calcium carbonate is 500nm.
The preparation method of the lithium metal graphene battery is characterized by comprising the following steps of:
step S1, uniformly mixing a titanium dioxide quantum dot/metallic lithium/fullerene compound, a conductive agent Super P and polyvinylidene fluoride PVDF according to a mass ratio of 8:1:1, then dripping N-methylpyrrolidone into the mixture, and uniformly stirring the mixture to form a viscous productThe thick pasty viscous liquid is uniformly coated on copper foil by a coating machine, and then compacted, and the coating surface density is 260g/m 2 Compact density 2.8g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then continuously slitting and continuously rolling to obtain a positive pole piece;
step S2, uniformly mixing the titanium dioxide quantum dot/metallic lithium/fullerene compound, the conductive agent Super P and PVDF according to a mass ratio of 8:1:1, then dripping N-methyl pyrrolidone into the mixture, uniformly stirring the mixture into thick uniform stable slurry by using double-planetary vacuum high-speed stirring equipment, and then stably and uniformly coating the prepared slurry on the surface of a copper foil by using an extrusion type double-sided coating machine, wherein the coating surface density is 220g/m 2 Compaction density of 1.8g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Then continuously slitting and continuously rolling to obtain a negative electrode plate;
step S3, uniformly mixing hyperbranched polyborosiloxane containing epoxy groups, melamine and nano calcium carbonate according to the weight ratio, carrying out melt extrusion and heat setting, then placing in a hydrochloric acid solution with the mass percentage concentration of 12% for soaking for 6 hours, taking out, washing with water for 6 times, and finally placing in a vacuum drying oven for drying at 95 ℃ until the weight is constant, thus obtaining the diaphragm;
and S4, assembling and injecting liquid to obtain the lithium metal graphene battery.
Comparative example 1
The formulation and preparation method of the super-capacity graphene battery are basically the same as those of the embodiment 1, except that no titanium dioxide quantum dots are added.
Comparative example 2
The formulation and preparation method of the super-capacity graphene battery are basically the same as those of the embodiment 1, except that no fullerene is added.
Comparative example 3
The formulation and preparation method of the super-capacity graphene battery are basically the same as those of the example 1, except that melamine is not added.
The lithium metal graphene batteries described in examples 1 to 5 and comparative examples 1 to 3 were charged at a 1.0C rate and discharged at a 1.0C rate at a temperature of 25±3 ℃ to perform cycle performance test, and the test results are shown in table 1.
TABLE 1
| Project | Cycle performance (capacity retention after 500 cycles),% | Energy Density (Wh/kg) |
| Example 1 | 97.1 | 184.3 |
| Example 2 | 97.3 | 184.7 |
| Example 3 | 97.4 | 184.9 |
| Example 4 | 97.7 | 185.3 |
| Example 5 | 97.9 | 185.5 |
| Comparative example 1 | 93.4 | 149.4 |
| Comparative example 2 | 93.9 | 150.6 |
| Comparative example 3 | 96.2 | 174.8 |
As can be seen from Table 1, the lithium metal graphene battery disclosed in the example of the present invention has a cycle performance (capacity retention rate after 500 cycles) of 97.1% or more, and a comparative example of 96.2% or less; the energy density is equal to or higher than 184.3Wh/kg, and the comparative example is equal to or lower than 174.8Wh/kg; thus, the example product has more excellent electrochemical stability, cycle performance and electrical properties.
Through tests, the products in the embodiments 1-5 of the invention can work within the range of-50 to +60 ℃, the storage life of the battery exceeds 12 years at normal temperature, no gas is separated out during the storage and discharge processes, and the safety performance is good.
While only a few embodiments of the present invention have been described, it should be noted that modifications could be made by those skilled in the art without departing from the principles of the present invention, which modifications are to be regarded as being within the scope of the invention.
Claims (6)
1. The super-capacity graphene battery is characterized in that the super-capacity graphene battery is a lithium metal graphene battery, and a positive electrode material of the lithium metal graphene battery is a nitrogen-doped nickel-cobalt-manganese-graphene composite; the negative electrode material of the lithium metal graphene battery is a titanium dioxide quantum dot/metal lithium/fullerene compound; the diaphragm of the lithium metal graphene battery is prepared from the following components in parts by weight: 50-60 parts of hyperbranched polyborosiloxane containing epoxy groups, 10-15 parts of melamine and 8-10 parts of nano calcium carbonate,
the preparation method of the hyperbranched polyborosiloxane containing epoxy groups comprises the following steps:
1) Under the conditions of stirring and nitrogen protection, adding 23.61g of gamma-glycidoxypropyl trimethoxysilane, 5.60g of boric acid, 5.15g of deionized water and 0.09g of 20% tetramethylammonium hydroxide solution into a three-neck flask, and refluxing at a constant temperature of 30 ℃ for 2 hours;
2) Adding 30.89g of trimethylchlorosilane, 18.00mL of methanol and 36.00mL of pyridine into the solution obtained in the step 1) under the conditions of stirring and nitrogen protection, refluxing at a constant temperature of 40 ℃ for 6 hours, and distilling under reduced pressure to obtain a crude product;
3) Finally, dissolving the crude product in 1g of dichloromethane, filtering out insoluble matters, and carrying out reduced pressure distillation and vacuum drying to obtain the hyperbranched polyborosiloxane;
the prepared hyperbranched polyborosiloxane has the viscosity of 400 mPas at 25 ℃ and has the following molecular formula:
[(CH3)3SiO1/2]a[R1R22SiO1/2]b[R1R2SiO2/2]c[R1SiO3/2]d
[R32BO1/2]e[R3BO2/2]h[BO3/2]k
wherein a+b+c+d=1, 0 < a < 1,0 < b < 1,0 < c < 1,0 < d < 1; e+h+k=1, 0 < e < 1,0 < h < 1,0 < k < 1; r1 is glycidoxypropyl, R2 is methoxy; r3 is hydroxy.
2. The super-capacity graphene battery according to claim 1, wherein the nitrogen-doped nickel-cobalt-manganese-graphene-based composite is a mixture formed by uniformly mixing nitrogen-doped nickel-cobalt-manganese ternary materials and graphene according to a mass ratio (3-5): 1.
3. The super-capacity graphene battery according to claim 1, wherein the titanium dioxide quantum dot/lithium metal/fullerene compound is a mixture formed by uniformly mixing titanium dioxide quantum dots, lithium metal and fullerene according to a mass ratio of 1 (4-6) (0.3-0.6).
4. The super-capacity graphene battery according to claim 1, wherein the electrolyte of the lithium metal graphene battery is a lithium hexafluorophosphate solution with a concentration of 0.8-1.2 mol/L.
5. The super-capacity graphene battery according to claim 4, wherein the solvent of the lithium hexafluorophosphate solution is a mixture formed by mixing ethylene carbonate and diethyl carbonate according to a mass ratio of 1 (3-5).
6. The super-capacity graphene battery of claim 1, wherein the nano calcium carbonate has a particle size of 200-500nm.
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