CN114772582A - Composite carbon material and application thereof in lithium ion battery - Google Patents
Composite carbon material and application thereof in lithium ion battery Download PDFInfo
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- CN114772582A CN114772582A CN202210427011.2A CN202210427011A CN114772582A CN 114772582 A CN114772582 A CN 114772582A CN 202210427011 A CN202210427011 A CN 202210427011A CN 114772582 A CN114772582 A CN 114772582A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 51
- 238000002360 preparation method Methods 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 33
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 32
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000008103 glucose Substances 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000006256 anode slurry Substances 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 10
- 239000002048 multi walled nanotube Substances 0.000 claims description 10
- 238000004806 packaging method and process Methods 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000003273 ketjen black Substances 0.000 claims description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- 239000011267 electrode slurry Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 abstract description 2
- 238000000498 ball milling Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 239000012528 membrane Substances 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 8
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002562 thickening agent Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- 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
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/582—Halogenides
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a composite carbon material, which comprises the following steps: dispersing carbon nanotubes, a surfactant and glucose in deionized water, and carrying out hydrothermal reaction to obtain hydrothermal carbon; and drying and carbonizing the hydrothermal carbon, mixing the carbonized hydrothermal carbon with potassium hydroxide, performing an activation reaction, washing with water to be neutral, and drying to obtain the composite carbon material. The invention also discloses the composite carbon material prepared by the preparation method and application of the composite carbon material in a lithium ion battery. When the carbon composite material disclosed by the invention is applied to a lithium ion battery taking LiI as a positive electrode material, the LiI can be adsorbed, the shuttle effect of the LiI in the battery is inhibited, the self-discharge of the lithium ion battery is reduced, and the rate characteristic and the cycle stability of the battery are improved; and a plurality of carbon materials are selected for combination, so that the contact between electrode active materials is greatly increased, the conductivity is improved, and the rapid charge and discharge of the battery are facilitated. The material used in the invention is easy to obtain, the preparation method is simple, and the industrial production is convenient.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a composite carbon material and application thereof in a lithium ion battery.
Background
Compared with other secondary batteries, lithium ion batteries have successfully led to the energy market due to their advantages of high energy density and good cycle stability. With the rapid development of the lithium ion battery industry, the market puts more stringent requirements on the rapid charge and discharge performance and the high and low temperature performance of the lithium ion battery, and the optimization of the anode material in the lithium ion battery is one of the important ways for improving the performance. The high nickel ternary is the mainstream development trend of the anode material of the lithium ion battery at present, but the further development of the high nickel ternary is restricted by the structural stability problem of the high nickel and the cost problem of rare metal cobalt.
Lithium iodide is used as one of the anode materials of the lithium ion battery, the stock is rich, the cost is low, and the influence of a conversion reaction type charge-discharge mechanism under the conditions of high multiplying power and high and low temperature charge-discharge is small. However, under the existing formula system, the lithium iodide used as the lithium ion battery anode material has the problems of poor conductivity, easy deliquescence, serious ion shuttling effect and the like, so that the search for a suitable formula system is urgent.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is that the lithium ion battery using lithium iodide as the anode material is adopted, so that the composite carbon material and the application thereof in the lithium ion battery are provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of a composite carbon material, which comprises the following steps:
s1: dispersing carbon nano tubes, a surfactant and glucose in deionized water, and then carrying out hydrothermal reaction to obtain hydrothermal carbon;
s2: drying and carbonizing the hydrothermal carbon, mixing the carbonized hydrothermal carbon with potassium hydroxide, and performing an activation reaction to obtain a rough composite carbon material;
s3: and washing the crude composite carbon material to be neutral, and drying to obtain the composite carbon material.
Furthermore, the diameter of the carbon nano tube is 5-20nm, and the length of the carbon nano tube is 5-15 μm;
the surfactant is Sodium Dodecyl Benzene Sulfonate (SDBS).
The mass ratio of the carbon nano tube to the surfactant to the glucose is 5-12:1: 800-1500.
In the step S1, the hydrothermal reaction temperature is 160-200 ℃, and the reaction time is 7-12 h;
in step S2, carbonization is carried out for reaction for 1-3h at 900 ℃ under the argon environment;
the activation reaction is 800-1000 ℃ for 1-3 h.
The invention also provides a composite carbon material prepared by the preparation method.
The invention also provides a lithium ion battery anode slurry which comprises the following raw materials in parts by mass:
80-90 parts of lithium iodide;
6-10 parts of conductive carbon;
4-10 parts of a binder;
the conductive carbon is a mixture of the composite carbon material and at least one of Ketjen Black (KB), carbon black (Super-P), multi-walled carbon nanotubes (MWCNT) or graphene (RGO), and the composite carbon material accounts for 20-80 wt% of the conductive carbon;
the binder is at least one of polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), vinylpyrrolidone-vinyl acetate copolymer (PVP-VA) or polyethylene glycol (PEG 2000).
The preparation method of the lithium ion battery anode slurry comprises the steps of fully dispersing lithium iodide in ethanol, and then mixing conductive carbon and a binder to obtain the lithium ion battery anode slurry, wherein the water content in the ethanol is less than 200 ppm.
The preparation method of the lithium ion battery positive pole piece comprises the steps of coating the lithium ion battery positive pole slurry on a current collector in an inert environment, and drying to obtain the lithium ion battery positive pole piece.
The invention also provides a lithium ion battery, which takes the lithium ion battery anode piece as an anode piece.
The preparation method of the lithium ion battery comprises the steps of packaging a dry electric core obtained by assembling the positive pole piece, the negative pole piece and the electrolyte, drying, injecting liquid, standing and forming to obtain the lithium ion battery.
The cathode pole piece can select a graphite cathode, a silicon-carbon cathode or lithium metal as a cathode, and the electrolyte is DOL/DME (1:1 vol.%) of 1M LiTFSI.
The scheme provided by the invention has the following advantages:
1. in the preparation process of the carbon composite material, hydrothermal carbon obtained by glucose through hydrothermal reaction is further carbonized to obtain carbon-coated carbon nano tubes, and the carbon-coated carbon nano tubes are activated by potassium hydroxide to obtain the carbon composite material with the specific surface area of 2500-4000m2A carbon composite material per gram.
2. When the carbon composite material provided by the invention is applied to a lithium ion battery taking LiI as a positive electrode material, the LiI in the electrode material can be adsorbed by the ultrahigh specific surface area of the carbon composite material, the shuttle effect of the LiI in the battery is inhibited, and the self-discharge of the lithium ion battery is reduced; the carbon nano tube in the composite material can improve the rate characteristic and the cycle stability of the lithium ion battery while improving the conductivity and the mechanical stability of the material.
3. According to the invention, multiple carbon materials are selected and combined, and carbon materials with different properties are compounded in multiple ways, so that the contact among electrode active materials is greatly increased, the conductivity is improved, and the lithium ion battery is convenient to charge and discharge quickly.
4. The material used in the invention is easy to obtain, the preparation method is simple, and the industrial production is convenient.
Detailed Description
The following examples are provided to better understand the present invention, not to limit the best mode, and not to limit the content and protection scope of the present invention, and any product that is the same or similar to the present invention and is obtained by combining the present invention with other features of the prior art and the present invention falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a composite carbon material, and a preparation method thereof comprises the following steps:
(1) weighing 0.1g of carbon nano tube, 10mg of sodium dodecyl benzene sulfonate and 10g of glucose, adding into 100ml of deionized water, and performing ultrasonic dispersion uniformly;
(2) pouring the uniformly dispersed carbon nanotube aqueous solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 190 ℃ for 10 hours to obtain hydrothermal carbon;
(3) drying hydrothermal carbon reacted in a hydrothermal kettle, transferring the hydrothermal carbon into a tubular furnace, introducing argon for protection, and carbonizing at 800 ℃ for 2 hours to obtain carbon-coated carbon nanotubes; uniformly mixing the carbon-coated carbon nano tube with potassium hydroxide according to the mass ratio of 1:5, transferring the mixture into a tubular furnace, and performing activation reaction at 800 ℃ for 1 hour to obtain a crude composite carbon material;
(4) and washing the crude composite carbon material to be neutral, and drying to obtain the composite carbon material.
The embodiment also provides a lithium ion battery anode slurry, and the preparation method comprises the following steps:
adding 80g of lithium iodide into a ball milling tank, carrying out ball milling for 20min, then adding 6g of Ketjen black, 2g of multi-walled carbon nanotubes, 2g of composite carbon material and 10g of polyvinylpyrrolidone powder, and continuing to carry out ball milling for 4h to obtain uniformly dispersed anode slurry with the solid content of 38 wt.%.
The embodiment also provides a lithium ion battery positive pole piece, and the preparation method comprises the following steps:
transferring the slurry to an inert environment glove box, coating the slurry on a stainless steel current collector in an inert environment, and drying to obtain the lithium ion battery positive pole piece.
The embodiment also provides a lithium ion battery, and the preparation method comprises the following steps:
mixing a negative active material graphite, conductive carbon black, a binder SBR, a thickening agent CMC and cyclic ester ethylene carbonate according to a mass ratio of 93.5:2:3:0.5:1, adding a deionized water solvent, fully and uniformly stirring to obtain a negative slurry, coating the negative slurry on a stainless steel current collector, and drying to obtain the lithium ion battery negative pole piece. And (3) stacking the positive pole piece, the isolating membrane and the negative pole piece in sequence, wrapping the battery cell by using an aluminum plastic membrane, injecting DOL/DME (1:1 vol.%) electrolyte containing 1M LiTFSI, and then packaging to obtain the finished lithium ion battery.
Example 2
The embodiment provides a composite carbon material, and the preparation method comprises the following steps:
(1) 0.1g of carbon nano tube, 10mg of sodium dodecyl benzene sulfonate and 10g of glucose are weighed and added into 100ml of deionized water, and the mixture is uniformly dispersed by ultrasonic;
(2) pouring the uniformly dispersed carbon nanotube aqueous solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 190 ℃ for 10 hours to obtain hydrothermal carbon;
(3) drying the hydrothermal carbon reacted in the hydrothermal kettle, transferring the hydrothermal carbon into a tube furnace, introducing argon for protection, and carbonizing at 800 ℃ for 2 hours to obtain carbon-coated carbon nanotubes; uniformly mixing the carbon-coated carbon nano tube with potassium hydroxide according to the mass ratio of 1:5, transferring the mixture into a tubular furnace, and performing activation reaction at 800 ℃ for 1 hour to obtain a crude composite carbon material;
(4) and washing the crude composite carbon material with water to be neutral, and drying to obtain the composite carbon material.
The embodiment also provides a lithium ion battery anode slurry, and the preparation method comprises the following steps:
adding 80g of lithium iodide into a ball milling tank, adding ethanol, carrying out ball milling for 20min, then adding 4g of Ketjen black, 2g of multi-walled carbon nanotubes, 4g of composite carbon material and 10g of polyvinylpyrrolidone powder, and continuing to carry out ball milling for 4h to obtain uniformly dispersed anode slurry with the solid content of 38 wt.%.
The embodiment also provides a lithium ion battery positive pole piece, and the preparation method comprises the following steps:
transferring the slurry to an inert environment glove box, coating the slurry on a stainless steel current collector in an inert environment, and drying to obtain the lithium ion battery positive pole piece.
The embodiment also provides a lithium ion battery, and the preparation method comprises the following steps:
mixing a negative active material graphite, conductive carbon black, a binder SBR, a thickening agent CMC and cyclic ester ethylene carbonate according to a mass ratio of 93.5:2:3:0.5:1, adding a deionized water solvent, fully and uniformly stirring to obtain a negative slurry, coating the negative slurry on a stainless steel current collector, and drying to obtain the lithium ion battery negative pole piece. And (3) sequentially stacking the positive pole piece, the isolating membrane and the negative pole piece, wrapping the battery core by using an aluminum plastic membrane, injecting DOL/DME (1:1 vol.%) electrolyte containing 1M LiTFSI, and then packaging to obtain the finished product of the lithium ion battery.
Example 3
The embodiment provides a composite carbon material, and the preparation method comprises the following steps:
(1) weighing 0.1g of carbon nano tube, 10mg of sodium dodecyl benzene sulfonate and 10g of glucose, adding into 100ml of deionized water, and performing ultrasonic dispersion uniformly;
(2) pouring the uniformly dispersed carbon nanotube aqueous solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 190 ℃ for 10 hours to obtain hydrothermal carbon;
(3) drying hydrothermal carbon reacted in a hydrothermal kettle, transferring the hydrothermal carbon into a tubular furnace, introducing argon for protection, and carbonizing at 800 ℃ for 2 hours to obtain carbon-coated carbon nanotubes; uniformly mixing the carbon-coated carbon nano tube with potassium hydroxide according to the mass ratio of 1:5, transferring the mixture into a tubular furnace, and performing activation reaction at 800 ℃ for 1 hour to obtain a crude composite carbon material;
(4) and washing the crude composite carbon material with water to be neutral, and drying to obtain the composite carbon material.
The embodiment also provides a lithium ion battery anode slurry, and the preparation method comprises the following steps:
adding 90g of lithium iodide into a ball milling tank, adding ethanol, carrying out ball milling for 20min, then adding 2g of Ketjen black, 2g of multi-walled carbon nanotube, 2g of composite carbon material, 3g of vinylpyrrolidone-vinyl acetate copolymer powder and 1g of polyethylene glycol powder, and continuing carrying out ball milling for 4h to obtain uniformly dispersed anode slurry with the solid content of 33 wt.%.
The embodiment also provides a lithium ion battery positive pole piece, and the preparation method comprises the following steps:
transferring the slurry to an inert environment glove box, coating the slurry on a stainless steel current collector in an inert environment, and drying to obtain the lithium ion battery positive pole piece.
The present embodiment also provides a lithium ion battery, and the preparation method includes:
mixing a negative active material graphite, conductive carbon black, a binder SBR, a thickening agent CMC and cyclic ester ethylene carbonate according to a mass ratio of 93.5:2:3:0.5:1, adding a deionized water solvent, fully and uniformly stirring to obtain a negative slurry, coating the negative slurry on a stainless steel current collector, and drying to obtain the lithium ion battery negative pole piece. And (3) sequentially stacking the positive pole piece, the isolating membrane and the negative pole piece, wrapping the battery core by using an aluminum plastic membrane, injecting DOL/DME (1:1 vol.%) electrolyte containing 1M LiTFSI, and then packaging to obtain the finished product of the lithium ion battery.
Example 4
The embodiment provides a composite carbon material, and the preparation method comprises the following steps:
(1) 0.1g of carbon nano tube, 10mg of sodium dodecyl benzene sulfonate and 10g of glucose are weighed and added into 100ml of deionized water, and the mixture is uniformly dispersed by ultrasonic;
(2) pouring the uniformly dispersed carbon nanotube aqueous solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 190 ℃ for 10 hours to obtain hydrothermal carbon;
(3) drying hydrothermal carbon reacted in a hydrothermal kettle, transferring the hydrothermal carbon into a tubular furnace, introducing argon for protection, and carbonizing at 800 ℃ for 2 hours to obtain carbon-coated carbon nanotubes; uniformly mixing the carbon-coated carbon nano tube with potassium hydroxide according to the mass ratio of 1:5, transferring the mixture into a tubular furnace, and performing activation reaction at 800 ℃ for 1 hour to obtain a crude composite carbon material;
(4) and washing the crude composite carbon material to be neutral, and drying to obtain the composite carbon material.
The embodiment also provides a lithium ion battery anode slurry, and the preparation method comprises the following steps:
adding 90g of lithium iodide into a ball milling tank, adding ethanol, carrying out ball milling for 20min, then adding 2g of Ketjen black, 1g of multi-walled carbon nanotube, 1g of graphene, 2g of composite carbon material, 3g of polyvinyl butyral powder and 1g of vinyl pyrrolidone-vinyl acetate copolymer powder, and continuing carrying out ball milling for 4h to obtain uniformly dispersed anode slurry with the solid content of 32 wt.%.
The embodiment also provides a lithium ion battery positive pole piece, and the preparation method comprises the following steps:
transferring the slurry to an inert environment glove box, coating the slurry on a stainless steel current collector in an inert environment, and drying to obtain the lithium ion battery positive pole piece.
The present embodiment also provides a lithium ion battery, and the preparation method includes:
mixing a negative active material graphite, conductive carbon black, a binder SBR, a thickening agent CMC and cyclic ester ethylene carbonate according to a mass ratio of 93.5:2:3:0.5:1, adding a deionized water solvent, fully and uniformly stirring to obtain a negative slurry, coating the negative slurry on a stainless steel current collector, and drying to obtain the lithium ion battery negative pole piece. And (3) sequentially stacking the positive pole piece, the isolating membrane and the negative pole piece, wrapping the battery core by using an aluminum plastic membrane, injecting DOL/DME (1:1 vol.%) electrolyte containing 1M LiTFSI, and then packaging to obtain the finished product of the lithium ion battery.
Example 5
The embodiment provides a composite carbon material, and a preparation method thereof comprises the following steps:
(1) 0.1g of carbon nano tube, 10mg of sodium dodecyl benzene sulfonate and 10g of glucose are weighed and added into 100ml of deionized water, and the mixture is uniformly dispersed by ultrasonic;
(2) pouring the uniformly dispersed carbon nanotube aqueous solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction at 190 ℃ for 10 hours to obtain hydrothermal carbon;
(3) drying the hydrothermal carbon reacted in the hydrothermal kettle, transferring the hydrothermal carbon into a tube furnace, introducing argon for protection, and carbonizing at 800 ℃ for 2 hours to obtain carbon-coated carbon nanotubes; uniformly mixing carbon-coated carbon nanotubes and potassium hydroxide according to the mass ratio of 1:5, transferring the mixture into a tubular furnace, and carrying out activation reaction at 800 ℃ for 1h to obtain a crude composite carbon material;
(4) and washing the crude composite carbon material with water to be neutral, and drying to obtain the composite carbon material.
The embodiment also provides a lithium ion battery anode slurry, and the preparation method comprises the following steps:
adding 90g of lithium iodide into a ball milling tank, adding ethanol, carrying out ball milling for 20min, then adding 1g of multi-walled carbon nanotubes, 1g of graphene, 4g of activated carbon coated carbon nanotube material, 3g of polyvinyl butyral powder and 1g of polyvinylpyrrolidone powder, and continuing to carry out ball milling for 4h to obtain uniformly dispersed anode slurry with the solid content of 30 wt.%.
The embodiment also provides a lithium ion battery positive pole piece, and the preparation method comprises the following steps:
transferring the slurry to an inert environment glove box, coating the slurry on a stainless steel current collector in an inert environment, and drying to obtain the lithium ion battery positive pole piece.
The present embodiment also provides a lithium ion battery, and the preparation method includes:
mixing a negative active material graphite, conductive carbon black, a binder SBR, a thickening agent CMC and cyclic ester ethylene carbonate according to a mass ratio of 93.5:2:3:0.5:1, adding a deionized water solvent, fully and uniformly stirring to obtain a negative slurry, coating the negative slurry on a stainless steel current collector, and drying to obtain the lithium ion battery negative pole piece. And (3) sequentially stacking the positive pole piece, the isolating membrane and the negative pole piece, wrapping the battery core by using an aluminum plastic membrane, injecting DOL/DME (1:1 vol.%) electrolyte containing 1M LiTFSI, and then packaging to obtain the finished product of the lithium ion battery.
Comparative example 1
The comparative example also provides a lithium ion battery anode slurry, and the preparation method comprises the following steps:
adding 80g of lithium iodide into a ball milling tank, adding ethanol, carrying out ball milling for 20min, then adding 10g of multi-walled carbon nanotubes and 10g of polyvinylpyrrolidone powder, and continuing carrying out ball milling for 4h to obtain uniformly dispersed anode slurry with the solid content of 38 wt.%.
The comparative example also provides a lithium ion battery positive pole piece, and the preparation method comprises the following steps:
transferring the slurry to an inert environment glove box, coating the slurry on a stainless steel current collector in an inert environment, and drying to obtain the lithium ion battery positive pole piece.
The comparative example also provides a lithium ion battery, and the preparation method comprises the following steps:
mixing a negative active material graphite, conductive carbon black, a binder SBR, a thickening agent CMC and cyclic ester ethylene carbonate according to a mass ratio of 93.5:2:3:0.5:1, adding a deionized water solvent, fully and uniformly stirring to obtain a negative slurry, coating the negative slurry on a stainless steel current collector, and drying to obtain the lithium ion battery negative pole piece. And (3) stacking the positive pole piece, the isolating membrane and the negative pole piece in sequence, wrapping the battery cell by using an aluminum plastic membrane, injecting DOL/DME (1:1 vol.%) electrolyte containing 1M LiTFSI, and then packaging to obtain the finished lithium ion battery.
Comparative example 2
The comparative example also provides a lithium ion battery anode slurry, and the preparation method comprises the following steps:
adding 90g of lithium iodide into a ball milling tank, adding ethanol, carrying out ball milling for 20min, then adding 6g of multi-walled carbon nanotubes and 4g of polyvinylpyrrolidone powder, and continuing carrying out ball milling for 4h to obtain uniformly dispersed anode slurry with the solid content of 38 wt.%.
The comparative example also provides a lithium ion battery positive pole piece, and the preparation method comprises the following steps:
and transferring the slurry into an inert environment glove box, coating the slurry on a stainless steel current collector in an inert environment, and drying to obtain the lithium ion battery positive pole piece.
The comparative example also provides a lithium ion battery, and the preparation method comprises the following steps:
mixing a negative active material graphite, conductive carbon black, a binder SBR, a thickening agent CMC and cyclic ester ethylene carbonate according to a mass ratio of 93.5:2:3:0.5:1, adding a deionized water solvent, fully and uniformly stirring to obtain a negative slurry, coating the negative slurry on a stainless steel current collector, and drying to obtain the lithium ion battery negative pole piece. And (3) sequentially stacking the positive pole piece, the isolating membrane and the negative pole piece, wrapping the battery core by using an aluminum plastic membrane, injecting DOL/DME (1:1 vol.%) electrolyte containing 1M LiTFSI, and then packaging to obtain the finished product of the lithium ion battery.
Test examples
The lithium ion batteries obtained in the examples and comparative examples were subjected to performance tests.
The test items include the charge and discharge tests of 0.3C, 1C, 5C and 10℃ at the normal temperature of 25 ℃ and the tests of 1C at the temperature of 0 ℃, 10 ℃, 20 ℃ and 30 ℃, and the test results are shown in tables 1 and 2.
TABLE 1 volume retention at different temperatures for each of the examples and comparative examples
TABLE 2 volume retention test for various turns of each example and comparative example
As can be seen from the above 2 tables, the lithium ion battery of the comparative example without the composite carbon material provided in the present application has far inferior low temperature performance and long cycle performance to the examples of the present application, which shows that the composite carbon material provided in the present application can improve the capacity retention rate of the lithium ion battery at low temperature and the capacity retention rate in the long cycle life test.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A preparation method of a composite carbon material is characterized by comprising the following steps:
s1: dispersing carbon nano tubes, a surfactant and glucose in deionized water, and then carrying out hydrothermal reaction to obtain hydrothermal carbon;
s2: drying and carbonizing the hydrothermal carbon, mixing the carbonized hydrothermal carbon with potassium hydroxide, and performing an activation reaction to obtain a crude composite carbon material;
s3: and washing the crude composite carbon material with water to be neutral, and drying to obtain the composite carbon material.
2. The method according to claim 1, wherein the carbon nanotube has a tube diameter of 5 to 20nm and a tube length of 5 to 15 μm;
the surfactant is sodium dodecyl benzene sulfonate.
3. The method according to claim 1 or 2, wherein the mass ratio of the carbon nanotubes, the surfactant and the glucose is 5-12:1: 800-1500.
4. The method according to any one of claims 1 to 3, wherein in step S1, the hydrothermal reaction temperature is 160-200 ℃, and the reaction time is 7-12 h;
in step S2, carbonization is carried out at 900 ℃ for 1-3h under the argon environment;
the activation reaction is 800-1000 ℃ for 1-3 h.
5. A composite carbon material produced by the production method according to any one of claims 1 to 4.
6. The lithium ion battery anode slurry is characterized by comprising the following raw materials in parts by mass:
80-90 parts of lithium iodide;
6-10 parts of conductive carbon;
4-10 parts of a binder;
the conductive carbon is the composite carbon material of claim 5 mixed with at least one of ketjen black, carbon black, multi-walled carbon nanotubes, or graphene, the composite carbon material comprising 20-80 wt.% of the conductive carbon;
the binder is at least one of polyvinyl butyral, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymer and polyethylene glycol.
7. The method for preparing a positive electrode slurry for a lithium ion battery as defined in claim 6, wherein lithium iodide is dispersed in ethanol sufficiently, and then conductive carbon and a binder are mixed to obtain the positive electrode slurry for a lithium ion battery.
8. A preparation method of a lithium ion battery positive pole piece is characterized in that the lithium ion battery positive pole slurry of claim 6 or the lithium ion battery positive pole slurry prepared by the preparation method of claim 7 is coated on a current collector in an inert environment and dried to obtain the lithium ion battery positive pole piece.
9. A lithium ion battery is characterized in that the lithium ion battery positive pole piece prepared by the preparation method of claim 8 is used as a positive pole piece.
10. The method for preparing the lithium ion battery of claim 9, wherein the lithium ion battery is obtained by packaging a dry electric core obtained by assembling the positive electrode plate, the negative electrode plate and the electrolyte, drying, injecting liquid, standing and forming.
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