CN113603132A - Carbon nano composite material and application thereof in battery - Google Patents
Carbon nano composite material and application thereof in battery Download PDFInfo
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- CN113603132A CN113603132A CN202110879980.7A CN202110879980A CN113603132A CN 113603132 A CN113603132 A CN 113603132A CN 202110879980 A CN202110879980 A CN 202110879980A CN 113603132 A CN113603132 A CN 113603132A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 36
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 51
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 50
- 238000002156 mixing Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005406 washing Methods 0.000 claims abstract description 38
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000010992 reflux Methods 0.000 claims description 29
- 239000002202 Polyethylene glycol Substances 0.000 claims description 27
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 229920001223 polyethylene glycol Polymers 0.000 claims description 27
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 27
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 11
- 239000010439 graphite Substances 0.000 abstract description 11
- 229910021382 natural graphite Inorganic materials 0.000 abstract description 6
- 239000002048 multi walled nanotube Substances 0.000 description 43
- 239000000203 mixture Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 230000007935 neutral effect Effects 0.000 description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- 229910003481 amorphous carbon Inorganic materials 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 241001388119 Anisotremus surinamensis Species 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000002931 mesocarbon microbead Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000011366 tin-based material Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000002946 graphitized mesocarbon microbead Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
- H01M2004/027—Negative electrodes
-
- 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 carbon nano composite material and application thereof in batteries, and the preparation method comprises the following steps: pretreating the carbon nano tube, and mixing with mixed acid to prepare an acidified carbon nano tube; reproducing SnO2(ii) a Mixing acidified carbon nanotubes withSnO2Mixing, adding into deionized water, ultrasonic dispersing, heating in water bath, dropping alkali liquor to make the solution alkaline, filtering and washing the solution to neutrality, sintering at low temperature, and then roasting at high temperature to obtain the carbon nano composite material. When the scanning voltage of the carbon nano composite material prepared by the invention is 0.02-2.5V and the current density is 25mA/g, the initial discharge capacity can reach 1800mAh/g (far larger than SnO)2200mAh/g of natural graphite and 372mAh/g of natural graphite), the capacity is still about 1710mAh/g after 3000 cycles, and the high-performance graphite has good cycle stability.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a carbon nano composite material and application thereof in batteries.
Background
The initial lithium battery cathode material is a lithium simple substance, but because dendritic crystals are formed in the charging and discharging process, the lithium battery cathode material has a serious safety problem and cannot be used for practical application. Currently, the most common negative electrode materials of lithium ion batteries include carbon materials, tin-based materials, silicon-based materials and the like.
The carbon material is the most commonly used negative electrode material in practical production at present because of the advantages of stable charge and discharge, low de-intercalated lithium potential (0.2-0.5V), good cycling stability of the battery, low price, abundant reserves and the like. The carbon material mainly comprises graphitized mesocarbon microbeads, natural graphite and amorphous carbon. The mesocarbon microbeads (MBMC) are used as the negative electrode material of the lithium battery, and the mesocarbon microbeads are spherical in microscopic morphology, so that the compact stacking can be realized, an electrode with higher density can be obtained, and meanwhile, the spherical surface also overcomes the defect of anisotropy of a graphite sheet layer. Therefore, people have made certain research and attention on the preparation, modification and charge-discharge mechanism of the mesocarbon microbead lithium battery negative electrode material.
When the natural graphite is used as a lithium battery negative electrode material, the specific capacity can reach the theoretical capacity 372mAh/g, but the actual specific capacity can be lower than the theoretical capacity because the shape, the particle size, the specific surface area, the crystal defects and the like of the graphite have great influence on the electrochemical performance of the electrode material. The graphite negative electrode material reacts with the electrolyte to form an SEI (solid electrolyte interface) film in the first charge-discharge process, and a part of lithium ions are consumed, so that the first coulombic efficiency is low; in addition, if the formed SEI film is not sufficiently dense, the electrolyte acts on the graphite material further, and the graphite sheet is likely to be peeled off or peeled off, thereby damaging the electrode material.
The structure of the amorphous carbon material consists of graphite microcrystals and amorphous areas, and a large number of nano holes are formed in the amorphous areas due to the escape of small molecules during heat treatment, so that the charge and discharge capacity of the amorphous carbon is larger than the theoretical capacity (372mAh/g) of graphite. However, the lithium battery stability of the amorphous carbon negative electrode material is poor, and the first charge-discharge efficiency is low. Meanwhile, the carbon negative electrode material has low theoretical capacity, so that the requirements of the modern society on high specific capacity and high energy density of the lithium ion battery are still difficult to meet even after modification, and the application of the carbon negative electrode material in the field of high current density is greatly limited.
Although the current commercial negative electrode material is mainly a carbon material, due to the defects of low theoretical specific capacity, low first charge-discharge efficiency, organic solvent co-intercalation and the like, people begin to research high-capacity non-carbon negative electrode materials, such as tin-based materials. At present, the research on tin-based materials mainly focuses on tin-based oxides, tin-based alloys, tin-based composite oxides and the like. SnO and SnO obtained by different preparation methods2The structure of (A) is different, and has crystalline, amorphous, nano-fibrous and nano-porous structures, etc., which have great influence on the electrochemical properties (such as specific capacity, cyclicity, etc.). Pure tin has high reactivity to lithium ions, but has severe volume expansion during charge and discharge, so that the cycle performance of the tin is reduced.
Disclosure of Invention
The invention aims to provide a carbon nano composite material with high specific capacity, high energy density and good cycling stability.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a carbon nano composite material, which comprises the following steps:
(1) firstly, pretreating a carbon nano tube, wherein the pretreatment process of the carbon nano tube comprises the steps of ultrasonically dispersing the carbon nano tube in a sodium hydroxide solution, washing after soaking, mixing the carbon nano tube with concentrated nitric acid, refluxing under an ultrasonic condition, mixing the pretreated carbon nano tube with mixed acid, refluxing, washing and drying to prepare an acidified carbon nano tube;
(2) SnCl4·5H2Mixing O and polyethylene glycol (PEG), dissolving in deionized water, ultrasonic dispersing, and dropwise adding ammonia water under stirring until SnCl4·5H2O is completely hydrolyzed, and SnO is obtained through suction filtration, washing and sintering2;
(3) Mixing acidified carbon nano-tube with SnO2Mixing, adding into deionized water, ultrasonic dispersing, heating in water bath, dropping alkali liquor to make the solution alkaline, filtering and washing the solution to neutrality, vacuum sintering at 90-110 deg.C for 5-8h, and roasting at 280-350 deg.C for 2-3h to obtain the carbon nano composite material.
Further, the carbon nanotube is a multi-walled carbon nanotube.
Because the carbon nano tube prepared by any method always contains a certain amount of impurities such as metal catalyst particles, amorphous carbon, nano carbon particles and the like, and subsequent application of the carbon nano tube is restricted, the multi-wall carbon nano tube is firstly soaked in a sodium hydroxide solution, ultrasonically dispersed, and then mixed with concentrated nitric acid for ultrasonic reflux treatment, so that on one hand, Van der Waals force between the multi-wall carbon nano tubes can be destroyed, agglomeration of the multi-wall carbon nano tube is avoided, on the other hand, the catalyst particles and part of amorphous carbon impurities can be fully dissolved, overlong carbon nano tubes are cut off, the purity of the multi-wall carbon nano tubes is improved, and after the long multi-wall carbon nano tubes are cut short, some functional groups with reaction activity, such as carboxyl, hydroxyl and the like, can be introduced into the end ports or the side walls of the multi-wall carbon nano tubes through acid treatment. The multi-walled carbon nano-tube after pretreatment almost has no impurities such as metal catalyst particles, amorphous carbon and the like, the purity can reach 98-99%, and the dispersibility and stability in water are obviously improved, thereby being beneficial to the preparation of composite materials.
Further, the ultrasonic power is 200-300W in the pretreatment process of the carbon nano tube in the step (1), the frequency is 40-50kHz, the reflux temperature is 80-90 ℃, and the reflux time is 8-10 h.
Further, the mixed acid in the step (1) is prepared from (5-7) by volume: 1 concentrated sulfuric acid and concentrated nitric acid.
Further, after the carbon nano tube pretreated in the step (1) is mixed with mixed acid, the reflux temperature is 70-80 ℃, and the reflux time is 3-4 h.
Further, step (2) SnCl4·5H2The mass ratio of O to polyethylene glycol is (2-10): 1. preferably the mass ratio is 2, 4, 8 or 10.
Further, PEG has a molecular weight of 1000, 2000, or 4000. The addition of PEG can promote crystal development, form long-range ordered structure, and reduce SnO2The grain size of (a). SnO obtained from PEG of different molecular weights2SnO obtained from PEG with different crystal grain shapes and sizes and molecular weight of 10002The size is between 150 and 300nm, the granularity is lower, and the particles are mainly spheroidal particles; PEG-derived SnO with molecular weight 20002The size is about 100 nm; SnO obtained from PEG with molecular weight of 40002The sphericity was similar to that of the molecular weight of 2000, and the size was further reduced to about 75 nm. When the molecular weight of PEG is too large or too small, the subsequent preparation of the composite material is not facilitated.
Further, the sintering temperature in the step (2) is 150-.
Further, acidifying the carbon nanotubes and SnO in step (3)2In a molar ratio of 1: (1-7).
Further, the temperature of the water bath in the step (3) is 70-80 ℃.
The invention also provides a carbon nano composite material prepared by the preparation method.
The invention also provides application of the carbon nano composite material in batteries, and the carbon nano composite material is used for preparing a lithium ion battery cathode material.
Due to sp2The existence of a hybrid C atom pi orbit enables planar carbon atoms of the wall of the carbon nano tube to have higher activity, the dispersibility of the carbon nano tube in an organic solvent and a polymer is changed through pretreatment, firstly, the surface of the carbon nano tube is oxidized by substances with oxidability to generate defects, then oxygen-containing groups such as carboxyl, hydroxyl and the like are introduced, the oxygen-containing groups are easier to perform subsequent reaction, and finally, a target product is formed.
The smooth surface of the tin dioxide can reduce side reactions on the surface of the electrode in the charging process, thereby improving the coulombic efficiency in the first charging process. The carbon nanotube, as an allotrope of graphite, has a graphitized structure, and has the disadvantages of the lithium ion battery prepared from some graphitized carbon materials, such as easy collapse, excessive swelling and the like. The multi-walled carbon nano tube has a layered structure similar to graphite, wherein gaps between the hollow tube and the tube are uniform and have nanometer sizes, and the multi-walled carbon nano tube has excellent lithium intercalation performance. The carbon nano composite material prepared by the invention is of a pompon structure formed by mutually connecting nano sheets, and lithium ions can be embedded and separated in all directions of the sphere due to the pompon lamellar structure, so that the problems of excessive swelling and collapse of graphite lamellar, incapability of large-current charging and discharging and the like caused by anisotropy of a graphitized carbon material are solved, the volume expansion of tin can be relieved by the pompon composite material, the tin particles are fully dispersed in the composite material, and sufficient buffer space is provided, so that the structural stability of an electrode is maintained, and the cycle stability is improved.
The invention discloses the following technical effects:
the carbon nano composite material prepared by the invention has a pompon structure, the size distribution is uniform, the average grain size is 30-40nm, and the addition of the multi-wall carbon nano tube can limit SnO by the hollow structure of the carbon nano tube2To produce smaller nanoparticlesAnd can also improve SnO2And the dispersibility of the carbon nano-tube, and agglomeration is avoided. When the scanning voltage of the carbon nano composite material prepared by the invention is 0.02-2.5V and the current density is 25mA/g, the initial discharge capacity can reach 1800mAh/g (far larger than SnO)2200mAh/g of natural graphite and 372mAh/g of natural graphite), the capacity is still about 1710mAh/g after 3000 cycles, and the high-performance graphite has good cycle stability.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The multi-wall carbon nano tube in the embodiment of the invention is obtained by purchasing, the diameter of the carbon nano tube is 8-45nm, the length of the carbon nano tube is 5-20 mu m, and the purity of the carbon nano tube is about 60%.
In the invention, the concentration of the concentrated nitric acid is 68 percent, and the concentration of the concentrated sulfuric acid is 70 percent, which are mass fractions.
The preparation process of the electrode slice comprises the following steps: weighing an active substance (the carbon nano composite materials prepared in each example and comparative example), a conductive agent (acetylene black) and a binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, putting the active substance, the conductive agent and the binder polyvinylidene fluoride (PVDF) into a small beaker, dropping N-methylpyrrolidone (NMP) into the beaker to serve as a solvent, and stirring the solvent into slurry; placing the slurry on a copper foil, uniformly coating the slurry into a sheet by using an automatic coating machine, and uniformly attaching the coating on the surface of the copper foil: putting the prepared electrode material coating into a drying oven, drying for 2h at 80 ℃, moving into a vacuum drying oven after drying, vacuum drying for 12h at 105 ℃, and further removing the solvent to completely remove the solvent; and (3) tabletting the dried copper foil, compacting by using a roll machine, increasing the tap density of the electrode material, then punching a circular electrode plate with the diameter of 13mm by using a sheet punching machine, taking out, weighing and placing in a glove box for later use.
The assembled battery is a CR2430 button type experimental battery, the battery is assembled in a glove box filled with Ar atmosphere, and the moisture in the glove box is controlled to be below 5ppm in the assembling process. The button cell takes a pure metal lithium sheet as a counter electrode and a reference electrode, the diameter of the lithium sheet is necessarily larger than the diameter of an electrode plate by 13mm, and the diameter of the lithium sheet adopted by the invention is 15.6 mm; a porous polypropylene film (Celgard2400) is taken as a diaphragm, and when the diaphragm is used, the diaphragm is punched into a diaphragm with the diameter equal to the inner diameter of the positive shell of the CR2430 type battery, namely 24 mm; 1mol LLIPF/EC + DMC + EMC (volume ratio 1:1:1) is used as electrolyte.
The assembling steps of the button type lithium ion battery are as follows: the opening surface of the positive electrode shell faces upwards and is arranged on the substrate; placing the electrode plate in the center of the positive plate, sucking the electrolyte by using a rubber head dropper, wetting the surface of the electrode plate, clamping a diaphragm, covering the electrode plate, sucking the electrolyte again, and completely wetting the surface of the diaphragm; sequentially clamping a lithium plate, a gasket and a spring piece, placing the lithium plate, the gasket and the spring piece at the center of the electrode shell, and strictly aligning, wherein all the steps need to be operated by using tweezers and can be finely adjusted; and then clamping the negative electrode shell with tweezers to cover, filling the negative electrode shell into a sealing bag for sealing, moving the battery out of a glove box, immediately pressurizing and sealing the battery by using a hydraulic sealing machine, wiping off residual electrolyte on the surface of the battery, and standing for 24 hours to perform electrochemical test.
Example 1
A method for preparing a carbon nanocomposite, comprising the steps of:
(1) firstly, pretreating a multi-walled carbon nanotube: ultrasonically dispersing a multi-walled carbon nanotube in a sodium hydroxide solution (the concentration is 0.50mg/mL, the same below) for 30min, soaking for 10h, washing, then mixing the multi-walled carbon nanotube with concentrated nitric acid (the concentration is 68 percent), putting the mixture into a single-neck flask, refluxing for 10h at 85 ℃ under the ultrasonic condition of the frequency of 40kHz and the ultrasonic power of 250W, mixing the pre-treated multi-walled carbon nanotube with mixed acid (concentrated sulfuric acid and concentrated nitric acid mixed in a volume ratio of 5: 1), refluxing for 4h at 70 ℃, washing with deionized water to be neutral, and drying for 10h at 60 ℃ to obtain an acidified carbon nanotube with the purity of 98 percent;
(2) 4.9084g SnCl4·5H2Dissolving O and PEG with molecular weight of 2000 in deionized water, and SnCl4·5H2The mass ratio of O to PEG is 2: 1, ultrasonically dispersing, and dropwise adding ammonia water under the stirring condition until SnCl4·5H2O is completely hydrolyzed, and SnO is obtained by suction filtration, washing and sintering at 150 DEG C2;
(3) Mixing acidified carbon nano-tube with SnO2According to a molar ratio of 1:1, adding the mixture into deionized water, performing ultrasonic dispersion for 0.5h at 200W, heating in a water bath at 70 ℃, dropwise adding 5mol/L sodium hydroxide solution to make the solution alkaline, filtering and washing the solution to be neutral, sintering in vacuum at 90 ℃ for 8h, and roasting at 280 ℃ for 3h to obtain the carbon nano composite material.
The carbon nano composite material prepared by the embodiment has good sphericity, the average particle size is about 102nm, the initial discharge capacity is 1500mAh/g when the scanning voltage is 0.02-2.5V and the current density is 25mA/g, and the capacity is still about 1300mAh/g after 3000 cycles.
Example 2
A method for preparing a carbon nanocomposite, comprising the steps of:
(1) firstly, pretreating a multi-walled carbon nanotube: ultrasonically dispersing a multi-walled carbon nanotube in a sodium hydroxide solution for 30min, soaking for 10h, washing, mixing the multi-walled carbon nanotube with concentrated nitric acid (the concentration is 68%), putting the mixture into a single-neck flask, refluxing for 9h at 80 ℃ under the ultrasonic condition that the frequency is 45kHz and the ultrasonic power is 200W, mixing the pre-treated multi-walled carbon nanotube with mixed acid (concentrated sulfuric acid and concentrated nitric acid mixed according to the volume ratio of 6: 1), refluxing for 3h at 75 ℃, washing with deionized water to be neutral, and drying for 10h at 60 ℃ to obtain an acidified carbon nanotube with the purity of 98%;
(2) 4.9084g SnCl4·5H2Dissolving O and PEG with molecular weight of 2000 in deionized water, and SnCl4·5H2The mass ratio of O to PEG is 2: 1, ultrasonically dispersing, and dropwise adding ammonia water under the stirring condition until SnCl4·5H2O is completely hydrolyzed, and SnO is obtained by suction filtration, washing and sintering at 180 DEG C2;
(3) Mixing acidified carbon nano-tube with SnO2According to a molar ratio of 1: 2, adding the mixture into deionized water, performing ultrasonic dispersion for 0.5h at 200W, heating in a water bath at 70 ℃, dropwise adding 5mol/L sodium hydroxide solution to make the solution alkaline, filtering and washing the solution to be neutral, sintering in vacuum at 100 ℃ for 6h, and roasting at 300 ℃ for 3h to obtain the carbon nano composite material.
The carbon nano composite material prepared by the embodiment has good sphericity, the average particle size is about 105nm, the initial discharge capacity is 1550mAh/g when the scanning voltage is 0.02-2.5V and the current density is 25mA/g, and the capacity is still about 1320mAh/g after 3000 cycles.
Example 3
A method for preparing a carbon nanocomposite, comprising the steps of:
(1) firstly, pretreating a multi-walled carbon nanotube: ultrasonically dispersing a multi-walled carbon nanotube in a sodium hydroxide solution for 30min, soaking for 10h, washing, mixing the multi-walled carbon nanotube with concentrated nitric acid (the concentration is 68%), putting the mixture into a single-neck flask, refluxing for 9h at 85 ℃ under the ultrasonic condition that the frequency is 45kHz and the ultrasonic power is 250W, mixing the pre-treated multi-walled carbon nanotube with mixed acid (concentrated sulfuric acid and concentrated nitric acid mixed according to the volume ratio of 6: 1), refluxing for 4h at 75 ℃, washing with deionized water to be neutral, and drying for 8h at 60 ℃ to obtain an acidified carbon nanotube with the purity of 99%;
(2) 4.9084g SnCl4·5H2Mixing O with PEG with molecular weight of 4000, dissolving in deionized water, and SnCl4·5H2The mass ratio of O to PEG is 8:1, ultrasonically dispersing, and dropwise adding ammonia water under the stirring condition until SnCl4·5H2O is completely hydrolyzed, and SnO is obtained by suction filtration, washing and sintering at 160 DEG C2;
(3) Mixing acidified carbon nano-tube with SnO2According to a molar ratio of 1: 3, adding the mixture into deionized water, performing ultrasonic dispersion for 0.5h at 200W, heating in a water bath at 70 ℃, dropwise adding 5mol/L sodium hydroxide solution to make the solution alkaline, filtering and washing the solution to be neutral, sintering in vacuum at 90 ℃ for 8h, and roasting at 280 ℃ for 3h to obtain the carbon nano composite material.
The carbon nano composite material prepared by the embodiment has good sphericity, the average particle size is about 75nm, the initial discharge capacity is 1800mAh/g when the scanning voltage is 0.02-2.5V and the current density is 25mA/g, and the capacity is still about 1710mAh/g after 3000 cycles.
Example 4
A method for preparing a carbon nanocomposite, comprising the steps of:
(1) firstly, pretreating a multi-walled carbon nanotube: ultrasonically dispersing a multi-walled carbon nanotube in a sodium hydroxide solution for 30min, soaking for 10h, washing, mixing the multi-walled carbon nanotube with concentrated nitric acid (the concentration is 68%), putting the mixture into a single-neck flask, refluxing for 8h at 80 ℃ under the ultrasonic condition that the frequency is 50kHz and the ultrasonic power is 300W, mixing the pre-treated multi-walled carbon nanotube with mixed acid (concentrated sulfuric acid and concentrated nitric acid mixed according to the volume ratio of 7: 1), refluxing for 4h at 70 ℃, washing with deionized water to be neutral, and drying for 10h at 60 ℃ to obtain an acidified carbon nanotube with the purity of 98%;
(2) 4.9084g SnCl4·5H2Dissolving O and PEG with molecular weight of 1000 in deionized water, and SnCl4·5H2The mass ratio of O to PEG is 2: 1, ultrasonically dispersing, and dropwise adding ammonia water under the stirring condition until SnCl4·5H2O is completely hydrolyzed, and SnO is obtained by suction filtration, washing and sintering at 200 DEG C2;
(3) Mixing acidified carbon nano-tube with SnO2According to a molar ratio of 1:1, adding the mixture into deionized water, performing ultrasonic dispersion for 0.5h at 200W, heating in a water bath at 70 ℃, dropwise adding 5mol/L sodium hydroxide solution to make the solution alkaline, filtering and washing the solution to be neutral, sintering in vacuum at 90 ℃ for 8h, and roasting at 280 ℃ for 3h to obtain the carbon nano composite material.
The carbon nano composite material prepared by the embodiment is spherical-like particles, the average particle size is between 150 and 300nm, the initial discharge capacity is 1300mAh/g when the scanning voltage is 0.02-2.5V and the current density is 25mA/g, and the capacity is still about 1100mAh/g after 3000 cycles.
Example 5
A method for preparing a carbon nanocomposite, comprising the steps of:
(1) firstly, pretreating a multi-walled carbon nanotube: ultrasonically dispersing a multi-walled carbon nanotube in a sodium hydroxide solution for 30min, soaking for 8h, washing, mixing the multi-walled carbon nanotube with concentrated nitric acid (the concentration is 68%), putting the mixture into a single-neck flask, refluxing for 8h at 85 ℃ under the ultrasonic condition that the frequency is 45kHz and the ultrasonic power is 250W, mixing the pre-treated multi-walled carbon nanotube with mixed acid (concentrated sulfuric acid and concentrated nitric acid mixed according to the volume ratio of 6: 1), refluxing for 3h at 80 ℃, washing with deionized water to be neutral, and drying for 8h at 60 ℃ to obtain an acidified carbon nanotube with the purity of 99%;
(2) 4.9084g SnCl4·5H2Mixing O with PEG with molecular weight of 4000, dissolving in deionized water, and SnCl4·5H2The mass ratio of O to PEG is 4: 1, ultrasonically dispersing, and dropwise adding ammonia water under the stirring condition until SnCl4·5H2O is completely hydrolyzed, and SnO is obtained by suction filtration, washing and sintering at 160 DEG C2;
(3) Mixing acidified carbon nano-tube with SnO2According to a molar ratio of 1: 3, adding the mixture into deionized water, performing ultrasonic dispersion for 0.5h at 200W, heating in a water bath at 70 ℃, dropwise adding 5mol/L sodium hydroxide solution to make the solution alkaline, filtering and washing the solution to be neutral, sintering in vacuum at 90 ℃ for 8h, and roasting at 280 ℃ for 3h to obtain the carbon nano composite material.
The carbon nano composite material prepared by the embodiment has good sphericity, the average particle size is about 78nm, the initial discharge capacity is 1750mAh/g when the scanning voltage is 0.02-2.5V and the current density is 25mA/g, and the capacity is still about 1610mAh/g after 3000 cycles.
Example 6
A method for preparing a carbon nanocomposite, comprising the steps of:
(1) firstly, pretreating a multi-walled carbon nanotube: ultrasonically dispersing a multi-walled carbon nanotube in a sodium hydroxide solution for 30min, soaking for 10h, washing, mixing the multi-walled carbon nanotube with concentrated nitric acid (the concentration is 68%), putting the mixture into a single-neck flask, refluxing for 9h at 85 ℃ under the ultrasonic condition that the frequency is 45kHz and the ultrasonic power is 250W, mixing the pre-treated multi-walled carbon nanotube with mixed acid (concentrated sulfuric acid and concentrated nitric acid mixed according to the volume ratio of 6: 1), refluxing for 4h at 75 ℃, washing with deionized water to be neutral, and drying for 8h at 60 ℃ to obtain an acidified carbon nanotube with the purity of 99%;
(2) 4.9084g SnCl4·5H2Mixing O with PEG with molecular weight of 4000, dissolving in deionized water, and SnCl4·5H2The mass ratio of O to PEG is 10: 1, ultrasonically dispersing, and dropwise adding ammonia water under the stirring condition until SnCl4·5H2O is completely hydrolyzed, and SnO is obtained by suction filtration, washing and sintering at 200 DEG C2;
(3) Mixing acidified carbon nano-tube with SnO2According to a molar ratio of 1: 7, mixing, adding into deionized water, performing ultrasonic dispersion for 0.5h at 200W, heating in water bath at 80 ℃, dropwise adding 5mol/L sodium hydroxide solution to make the solution alkaline, filtering and washing the solution to be neutral, performing vacuum sintering at 110 ℃ for 5h, and roasting at 320 ℃ for 2h to obtain the carbon nano composite material.
The carbon nano composite material prepared by the embodiment has good sphericity, the average particle size is about 80nm, the initial discharge capacity is 1720mAh/g when the scanning voltage is 0.02-2.5V and the current density is 25mA/g, and the capacity is about 1580mAh/g after 3000 cycles.
Comparative example 1
A method for preparing a carbon nanocomposite, which is the same as example 3, except that the multi-walled carbon nanotube is first pretreated in step (1): mixing a multi-walled carbon nanotube with concentrated nitric acid (the concentration is 68 percent), putting the mixture into a single-neck flask, refluxing for 9h at 85 ℃ under the ultrasonic conditions of the frequency of 45kHz and the ultrasonic power of 250W, then mixing the pre-treated multi-walled carbon nanotube with concentrated sulfuric acid, refluxing for 4h at 75 ℃, washing the mixture to be neutral by deionized water, and drying the mixture for 8h at 60 ℃ to obtain the acidified carbon nanotube with the purity of 80 percent.
The carbon nano composite material prepared by the comparative example is in a sphere-like shape, the average particle size is 200-300nm, the initial discharge capacity is 750mAh/g when the scanning voltage is 0.02-2.5V and the current density is 25mA/g, and the capacity is 650mAh/g after 300 cycles.
Comparative example 2
The only difference from example 3 is that the molecular weight of PEG is 6000.
The carbon nano composite material prepared by the comparative example has initial discharge capacity of 627mAh/g when scanning voltage is 0.02-2.5V and current density is 25mA/g, and has capacity of 423mAh/g after 200 cycles.
Comparative example 3
A method for preparing a carbon nanocomposite, comprising the steps of:
(1) firstly, pretreating a multi-walled carbon nanotube: ultrasonically dispersing a multi-walled carbon nanotube in a sodium hydroxide solution for 30min, soaking for 10h, washing, mixing the multi-walled carbon nanotube with concentrated nitric acid (the concentration is 68%), putting the mixture into a single-neck flask, refluxing for 8h at 90 ℃ under the ultrasonic condition that the frequency is 45kHz and the ultrasonic power is 300W, mixing the pre-treated multi-walled carbon nanotube with mixed acid (concentrated sulfuric acid and concentrated nitric acid mixed according to the volume ratio of 6: 1), refluxing for 4h at 75 ℃, washing with deionized water to be neutral, and drying for 8h at 60 ℃ to obtain an acidified carbon nanotube with the purity of 99%;
(2) 4.9084g SnCl4·5H2Mixing O with PEG with molecular weight of 4000, dissolving in deionized water, and SnCl4·5H2The mass ratio of O to PEG is 8:1, ultrasonically dispersing, and dropwise adding ammonia water under the stirring condition until SnCl4·5H2O is completely hydrolyzed, and SnO is obtained by suction filtration, washing and sintering at 160 DEG C2;
(3) Mixing acidified carbon nano-tube with SnO2According to a molar ratio of 1: 3, adding the mixture into deionized water, performing ultrasonic dispersion for 0.5h at 200W, heating in a water bath at 70 ℃, dropwise adding 5mol/L sodium hydroxide solution to make the solution alkaline, filtering and washing the solution to be neutral, and roasting at 280 ℃ for 11h to obtain the carbon nano composite material.
The carbon nano composite material prepared by the comparative example has initial discharge capacity of 720mAh/g when the scanning voltage is 0.02-2.5V and the current density is 25mA/g, and the capacity is about 410mAh/g after 100 cycles.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A method for preparing a carbon nanocomposite, comprising the steps of:
(1) firstly, pretreating a carbon nano tube, wherein the pretreatment process of the carbon nano tube comprises the steps of ultrasonically dispersing the carbon nano tube in a sodium hydroxide solution, washing after soaking, mixing the carbon nano tube with concentrated nitric acid, refluxing under an ultrasonic condition, mixing the pretreated carbon nano tube with mixed acid, refluxing, washing and drying to prepare an acidified carbon nano tube;
(2) SnCl4·5H2Mixing O and polyethylene glycol, dissolving in deionized water, ultrasonically dispersing, and dropwise adding ammonia water under stirring until SnCl4·5H2O is completely hydrolyzed, and SnO is obtained through suction filtration, washing and sintering2;
(3) Mixing acidified carbon nano-tube with SnO2Mixing, adding into deionized water, ultrasonic dispersing, heating in water bath, dropping alkali liquor to make the solution alkaline, filtering and washing the solution to neutrality, vacuum sintering at 90-110 deg.C for 5-8h, and roasting at 280-350 deg.C for 2-3h to obtain the carbon nano composite material.
2. The method as claimed in claim 1, wherein the ultrasonic power of the pretreatment process of the carbon nanotubes in step (1) is 200- "300W", the frequency is 40-50kHz, the reflux temperature is 80-90 ℃, and the reflux time is 8-10 h.
3. The preparation method according to claim 1, wherein the mixed acid in the step (1) is prepared by mixing (5-7): 1 concentrated sulfuric acid and concentrated nitric acid.
4. The preparation method according to claim 1, wherein the carbon nanotubes pretreated in step (1) are mixed with mixed acid, and then the reflux temperature is 70-80 ℃ and the reflux time is 3-4 h.
5. The method according to claim 1, wherein the step (2) of SnCl4·5H2The mass ratio of O to polyethylene glycol is (2-10): 1.
6. the method as claimed in claim 1, wherein the sintering temperature in step (2) is 150-200 ℃.
7. The method according to claim 1, wherein the step (3) of acidifying the carbon nanotubes and SnO2In a molar ratio of 1: (1-7).
8. The method of claim 1, wherein the temperature of the water bath in step (3) is 70 to 80 ℃.
9. A carbon nanocomposite produced by the production method according to any one of claims 1 to 8.
10. Use of the carbon nanocomposite according to claim 9 in batteries for the preparation of negative electrode materials for lithium ion batteries.
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