CN115246638B - Preparation method and application of hollow mesoporous carbon sphere with inner surface being wrinkled - Google Patents
Preparation method and application of hollow mesoporous carbon sphere with inner surface being wrinkled Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 40
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 38
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000005011 phenolic resin Substances 0.000 claims abstract description 28
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 28
- 238000005530 etching Methods 0.000 claims abstract description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000007773 negative electrode material Substances 0.000 claims abstract description 17
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 230000002441 reversible effect Effects 0.000 claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 91
- 239000000843 powder Substances 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 33
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000012360 testing method Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 239000000839 emulsion Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 11
- 239000008098 formaldehyde solution Substances 0.000 claims description 11
- 239000003607 modifier Substances 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 230000037303 wrinkles Effects 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- 239000004064 cosurfactant Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 6
- 238000000643 oven drying Methods 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 abstract description 43
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract description 43
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 abstract description 43
- 238000012986 modification Methods 0.000 abstract description 12
- 230000004048 modification Effects 0.000 abstract description 12
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 abstract description 12
- 238000011068 loading method Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 239000011149 active material Substances 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 36
- 238000001878 scanning electron micrograph Methods 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 229910052593 corundum Inorganic materials 0.000 description 14
- 239000010431 corundum Substances 0.000 description 14
- 229910052573 porcelain Inorganic materials 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 13
- 239000010406 cathode material Substances 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000000975 co-precipitation Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000005543 nano-size silicon particle Substances 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010294 electrolyte impregnation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 238000002604 ultrasonography 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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 relates to a preparation method and application of a hollow mesoporous carbon sphere with a wrinkled inner surface, belonging to the fields of nano materials and new energy materials. The invention adopts dendritic fiber type nano SiO 2 And (3) taking (DFNS) as a sacrificial template, modifying by polyvinylpyrrolidone (PVP), coating by using phenolic resin, simultaneously adding tetraethyl silicate (TEOS) to introduce mesopores, annealing, and etching by hydrofluoric acid (HF) to remove the sacrificial template to obtain the hollow mesoporous carbon spheres (IW-MHCS) with the inner surface wrinkled. The hollow mesoporous carbon sphere (IW-MHCS) with the wrinkled inner surface has higher reversible specific capacity and excellent cycle stability when being used for a negative electrode material of a potassium ion battery. The skillful design of the external smooth inner folds avoids excessive side reaction caused by large-area contact of the electrolyte and the carbon material, and improves the utilization rate of the active material. In addition, hollow mesoporous carbon spheres with folds on the inner surface are used as a matrix for metal loading, doping modification and other aspectsThe surface also has good application prospect, thus having a certain research value.
Description
Technical Field
The invention belongs to the technical field of nano materials and new energy materials, and particularly relates to a preparation method and application of hollow mesoporous carbon spheres with inner surface wrinkles.
Background
With the increasing application of rechargeable Lithium Ion Batteries (LIBs), the uneven distribution of lithium resources and the gradual increase of cost severely limit the application in large scale, especially in the application of electric automobiles in large scale. To address this problem, the search for alternative battery systems has focused on elements on earth that are rich in resources. Among candidates, potassium Ion Batteries (PIBs) are attracting attention due to low cost and abundant resources. In addition, K has a relatively close redox potential (-2.936V vs. Standard Hydrogen Electrode (SHE)) compared to lithium (-3.04V), which means that in theory PIBs should exhibit higher energy densities than LIBs. Nevertheless, due to K + Radius of greater than Li + />Thus, there is still a large gap between theoretical values, eventually impeding K + Embedded in the electrode material.
Recently, by utilizing pseudocapacitance effect in a battery system, extremely high rate performance is obtained. Resorcinol Formaldehyde (RF) is used as a carbon source, and K with dominant pseudocapacitance effect is realized in the hollow carbon nanospheres + And storing the behavior. Hollow carbon nanospheres enhance pseudocapacitive behavior and specific capacity, especially at high current densities. Obviously, the hollow porous material with the layered structure is favorable for improving electrochemical performance, the layered porous material is favorable for electrolyte impregnation, and the hollow structure can relieve volume expansion and ensure cycle stability. Further increasing the potassium ion storage sites often requires increasing the specific surface area of the hollow carbon material, and also increases the contact area between the carbon material and the electrolyte, resulting in side reactionsThe formation of a large-area SEI film should be aggravated, resulting in a decrease in the active material usage rate.
In order to improve the potassium ion storage site and reduce the contact area of the active material and the electrolyte, the smart design of the invention realizes the hollow mesoporous carbon sphere with smooth inner surface folds and smooth outer surface, the inner specific surface area can be increased by the fold design of the inner surface, and the loss of active materials caused by excessive contact with the electrolyte is avoided under the protection of the outer surface. In addition, the hollow mesoporous carbon spheres with inner folds can not only enlarge the wonderful colors on chemical energy storage, but also have great application prospects in serving as a drug carrying, microwave absorption and organic matter degradation matrix.
Disclosure of Invention
The invention provides a preparation method and application of hollow mesoporous carbon spheres with inner surface folds, which are designed and synthesized to have high inner specific surface area, uniform size, uniform specification, inner folds and smooth outside, and research on electrochemical properties of the hollow mesoporous carbon spheres, in order to improve potassium ion storage sites and reduce the contact area of active materials and electrolyte at the same time so as to solve the key problems of low coulomb efficiency, low specific charge-discharge capacity, poor cycle stability and the like when the traditional carbon material is used as a potassium ion negative electrode material. The comprehensive electrochemical performance of the material is effectively improved by a simple synthesis method.
The technical scheme adopted for solving the technical problems is as follows: preparation method of hollow mesoporous carbon sphere with inner surface wrinkles adopts dendritic fiber-shaped nano SiO 2 And (3) taking (DFNS) as a sacrificial template, modifying by polyvinylpyrrolidone (PVP), coating by using phenolic resin, simultaneously adding tetraethyl silicate (TEOS) to introduce mesopores, annealing, and etching by hydrofluoric acid (HF) to remove the sacrificial template to obtain the hollow mesoporous carbon spheres (IW-MHCS) with the inner surface wrinkled.
Further, the preparation method comprises the following steps:
step (1): cetyl Trimethyl Ammonium Bromide (CTAB), isopropanol and urea are taken and dissolved in a cyclohexane and water mixed solution to obtain a solution A;
step (2): adding tetraethyl silicate (TEOS) into the solution A dropwise, and reacting at 60-80 ℃ for 12-20h to obtain a white product B;
step (3): dispersing the white product B in absolute ethyl alcohol, adding hydrochloric acid to remove residual CTAB, and reacting at 60-80 ℃ for 18-30h to obtain DFNS;
step (4): dispersing DFNS as a sacrificial template into water, adding PVP surface modifier to obtain white product PVP dispersed DFNS, namely P-DFNS;
dispersing the P-DFNS in water, adding resorcinol and formaldehyde, then adding ammonia water, then dropwise adding TEOS, and reacting for 2-4 hours at 50-80 ℃ to obtain a phenolic resin coated P-DFNS brown product which is marked as P-DFNS@RF;
Annealing the P-DFNS@RF under a protective atmosphere to carbonize the phenolic resin to obtain a black product, which is marked as P-DFNS@C;
and (7) dispersing the P-DFNS@C into an HF solution, etching to remove the P-DFNS, and carrying out suction filtration and drying to obtain the hollow mesoporous carbon spheres (IW-MHCS) with the inner surface wrinkled black products.
Further, the preparation method comprises the following specific steps of:
step (1): taking 1-3.0g of Cetyl Trimethyl Ammonium Bromide (CTAB) as a surfactant, 1-3ml of isopropanol as a cosurfactant and urea with the mass ratio of CTAB of 0.6:1, dissolving the urea into 120-150ml of cyclohexane and water mixed solution, and stirring the mixture uniformly at room temperature to obtain solution A; wherein the volume ratio of cyclohexane to water is (5-7): (5-7);
step (2): tetraethyl silicate (TEOS) is added into the solution A dropwise in an amount of 1/20 of the volume of the solution A, and the reaction is carried out for 12-20h at 60-80 ℃; centrifuging the obtained emulsion solution, washing and drying to obtain a white product B;
step (3): dispersing 0.3-1g of white product B in 200-300mL of absolute ethyl alcohol, adding 15-20mL of hydrochloric acid to remove residual CTAB, reacting at 60-80 ℃ for 18-30h, centrifuging the obtained emulsion solution, washing and drying to obtain DFNS;
Step (4): dispersing 0.5-1g of DFNS serving as a sacrificial template into 240-300ml of water, adding 2-3g of PVP surface modifier, stirring to obtain a turbid solution, centrifuging, washing and drying to obtain white product PVP dispersed DFNS, namely P-DFNS;
dispersing 0.3-0.6-g P-DFNS in 180-360ml of water, stirring and dispersing uniformly by ultrasonic, adding 0.15-0.75g of resorcinol and 0.21-1.05ml of formaldehyde solution, then adding 400-500 mu l of ammonia water, and then dropwise adding TEOS, wherein the mass volume ratio g of resorcinol to TEOS is (1-3); reacting the mixed solution at 50-80 ℃ for 2-4 hours to obtain a brown turbid solution, and performing centrifugal separation, washing and drying to obtain a phenolic resin coated P-DFNS brown product, which is marked as P-DFNS@RF;
annealing the P-DFNS@RF in a protective atmosphere at 600-1000 ℃, and preserving heat for 2-6 hours to carbonize the phenolic resin to obtain a black product, which is denoted as P-DFNS@C;
and (7) dispersing the P-DFNS@C into an HF solution, etching to remove the P-DFNS, and carrying out suction filtration and drying to obtain the hollow mesoporous carbon spheres (IW-MHCS) with the inner surface wrinkled black products.
Further, in the steps (2), (3), (4) and (5), the drying temperature is 50-80 ℃ and the drying time is 10-20h.
Further, in the step (3), the hydrochloric acid concentration is 12M.
Further, in the step (3), heating is performed under stirring, condensing and refluxing conditions.
Further, in the step (4), the stirring time is 12 hours.
Further, in the step (4), the molecular weight of PVP is 8000-200000.
Further, in the step (5), the mass concentration of the formaldehyde solution is 37%.
Further, in the step (5), the mass concentration of the ammonia water is 25-28%.
Further, in the step (6), the annealing temperature rising rate is 2-8 ℃/min, and the protective atmosphere is argon (purity > 99 v%) or nitrogen (purity > 99 v%).
Further, in the step (7), the concentration of the HF solution is 10-30wt%, the etching time is 4-24 hours, and stirring ultrasonic and the like can be used for promoting etching in the etching process.
Further, in the step (7), the hollow mesoporous carbon spheres with the wrinkled inner surface are in a powder state, the appearance is spherical, the thickness of a carbon layer is 10-50nm, the particle size is 400-600nm, the outer surface is a smooth surface, the inner surface is a wrinkled surface, the ravines are vertical and horizontal and very rough, the surface of the carbon layer is distributed with mesopores (through holes), the diameter of each mesopore is 3-20nm, and the specific surface area of the carbon sphere is 400-700m 2 /g。
The invention also provides application of the hollow mesoporous carbon sphere prepared by the preparation method of the hollow mesoporous carbon sphere with the wrinkled inner surface as a cathode material of a potassium ion battery.
Further, the application of the hollow mesoporous carbon sphere prepared by the preparation method of the hollow mesoporous carbon sphere with the wrinkled inner surface as a cathode material of a potassium ion battery comprises the following specific steps:
(1) According to the mass percentage of each component, 70-80% of hollow mesoporous carbon spheres with wrinkles on the inner surface, 10-15% of acetylene black and 10-15% of binder are mixed and magnetically stirred for 2-4 hours to obtain slurry;
(2) Coating the slurry on the surface of a copper foil, wherein the coating thickness is 100-150 mu m, and vacuum drying to prepare a potassium ion battery negative plate;
(3) And (3) taking the metal potassium sheet as a battery positive plate, assembling the battery, and testing the electrochemical performance of the battery.
Further, in the step (1), the binder is PVDF.
Further, in the step (2), the battery is a button cell battery.
Further, in the step (3), the voltage adopted for testing the electrochemical performance of the battery is 0.01-3.0V, and the reversible capacity is kept between 110 mAh/g and 350mAh/g after 500 cycles under the current density of 1000 mA/g.
Compared with the prior art, the invention has the beneficial effects that:
The invention adopts dendritic fiber type nano SiO 2 (DFNS) as sacrificial template, modified and regulated by polyvinyl pyrrolidone (PVP) for regulating and controlling the coating amount of phenolic resinThe synthesis condition of the sacrificial template achieves the aim of controlling the appearance of the hollow mesoporous carbon sphere with the inner surface wrinkled. Through characterization data analysis, the regulation and control of the phenolic resin coating amount, PVP molecular mass and DFNS sacrificial template synthesis conditions have obvious influence on the appearance of IW-MHCS; the invention designs and synthesizes the inner pleat hollow mesoporous carbon sphere with high specific surface area, uniform size, uniform specification, smooth inner pleat and smooth outer, and researches the electrochemical performance of the carbon sphere. The comprehensive electrochemical performance of the material is effectively improved by a simple synthesis method. And the repeatability is high, the cost is low, the production period is short, the popularization is convenient, and the industrial production is realized.
The IW-MHCS provided by the invention has higher reversible specific capacity and excellent cycle stability when being used for a negative electrode material of a potassium ion battery. The skillful design of the external smooth inner folds avoids excessive side reaction caused by large-area contact of the electrolyte and the carbon material, and improves the utilization rate of the active material. The existence of the mesopores is beneficial to the substances entering the carbon sphere from the outside and the rapid exchange of the substances. In addition, the hollow mesoporous carbon sphere with the wrinkled inner surface is used as a matrix, and has good application prospect in the aspects of metal loading, doping modification and the like, so that the hollow mesoporous carbon sphere has a certain research value.
Drawings
FIG. 1 is an SEM image of an inner surface crimped hollow mesoporous carbon sphere (IW-MHCS 0.21/0.21) powder prepared in example 1;
FIG. 2 is an XRD pattern of inner surface crimped hollow mesoporous carbon spheres (IW-MHCS 0.21/0.21) powder prepared in example 1;
FIG. 3 is a graph showing the particle size distribution of the inner surface crimped hollow mesoporous carbon sphere (IW-MHCS 0.21/0.21) powder prepared in example 1;
FIG. 4 is a cycle chart of the inner surface corrugated hollow mesoporous carbon spheres (IW-MHCS 0.21/0.21) prepared in example 1 as a negative electrode material for a potassium ion battery at a current density of 1000 mA/g;
FIG. 5 is an SEM image of an inner surface crimped hollow mesoporous carbon sphere (IW-MHCS 0.255/0.255) powder prepared in example 2;
FIG. 6 is a graph showing the particle size distribution of the inner surface crimped hollow mesoporous carbon spheres (IW-MHCS 0.255/0.255) powder prepared in example 2;
FIG. 7 is a cycle chart of the inner surface corrugated hollow mesoporous carbon spheres (IW-MHCS 0.255/0.255) prepared in example 2 as a negative electrode material for a potassium ion battery at a current density of 1000 mA/g;
FIG. 8 is an SEM image of an inner surface crimped hollow mesoporous carbon sphere (IW-MHCS 0.3/0.3) powder prepared in example 3;
FIG. 9 is a graph showing the particle size distribution of the inner surface crimped hollow mesoporous carbon spheres (IW-MHCS 0.3/0.3) powder prepared in example 3;
FIG. 10 is a cycle chart of the inner surface corrugated hollow mesoporous carbon spheres (IW-MHCS 0.3/0.3) prepared in example 3 as a negative electrode material for a potassium ion battery at a current density of 1000 mA/g;
FIG. 11 is an SEM image of an inner surface crimped hollow mesoporous carbon sphere (0-IW-MHCS) powder prepared using a sacrificial template that was not PVP treated in example 4;
FIG. 12 is a cycle chart of example 4 using hollow mesoporous carbon spheres (0-IW-MHCS) with inner surface folds prepared from a sacrificial template without PVP treatment as a negative electrode material for a potassium ion battery at a current density of 1000 mA/g;
FIG. 13 is an SEM image of an inner surface crimped hollow mesoporous carbon sphere (58000-IW-MHCS) powder prepared using a sacrificial template treated with 58000 molecular weight PVP of example 5;
FIG. 14 is a cycle chart of an inner surface corrugated hollow mesoporous carbon sphere (58000-IW-MHCS) prepared using a sacrificial template treated with 58000 molecular weight PVP of example 5 as a negative electrode material for a potassium ion battery at a current density of 1000 mA/g;
FIG. 15 is an SEM image of DFNS powder prepared in examples 3, 6, and 7;
FIG. 16 is a BET spectrum of DFNS 7/5 prepared by adjusting the water-to-oil ratio in example 6;
FIG. 17 is a BJH pattern of DFNS 7/5 prepared by adjusting the water-to-oil ratio in example 6;
FIG. 18 is a BET spectrum of hollow mesoporous carbon sphere (C7/5) powder of example 6 with the inner surface folds obtained by adjusting the water-to-oil ratio of the prepared DFNS 7/5 as a sacrificial template;
FIG. 19 is a BJH spectrum of the inner surface corrugated hollow mesoporous carbon sphere (C7/5) powder of example 6 using DFNS 7/5 prepared by adjusting the water-to-oil ratio as a sacrificial template;
FIG. 20 is a cycle chart of a prepared inner surface corrugated hollow mesoporous carbon sphere (C7/5) as a negative electrode material of a potassium ion battery at a current density of 1000mA/g obtained by adjusting the water-to-oil ratio of the prepared DFNS 7/5 as a sacrificial template in example 6;
FIG. 21 is a BET spectrum of DFNS5/7 prepared by adjusting the water-to-oil ratio in example 7;
FIG. 22 is a BJH spectrum of DFNS5/7 prepared by adjusting the water-to-oil ratio in example 7;
FIG. 23 is a BET spectrum of hollow mesoporous carbon sphere (C5/7) powder of the inner surface wrinkles obtained in example 7 using DFNS5/7 prepared by adjusting the water-to-oil ratio as a sacrificial template;
FIG. 24 is a BJH spectrum of the inner surface corrugated hollow mesoporous carbon sphere (C5/7) powder of example 7 using DFNS5/7 prepared by adjusting the water-to-oil ratio as a sacrificial template;
FIG. 25 is a graph showing the cycle of the prepared inner surface corrugated hollow mesoporous carbon spheres (C5/7) obtained as a sacrificial template in example 7 using the DFNS5/7 prepared by adjusting the water-to-oil ratio as a cathode material for a potassium ion battery at a current density of 1000 mA/g.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The IW-MHCS 0.21/0.21 inner surface corrugated hollow mesoporous carbon sphere potassium ion battery cathode material is compounded by the modes of coprecipitation, polycondensation, modification, heat treatment, etching and washing filtration of raw materials.
The preparation method of the hollow mesoporous carbon sphere with the wrinkled inner surface comprises the following steps of:
step (1): cetyl trimethylammonium bromide (CTAB) (2.0 g), urea (1.2 g), isopropyl alcohol (1.84 mL), cyclohexane (60 mL) and deionized water (60 mL) were mixed in a three-necked flask and stirred at room temperature for 4 hours to give a solution A.
Step (2): tetraethyl silicate (TEOS) (6.0 mL) was added dropwise to solution a and placed in an oil bath at 70 ℃ for 16h under stirring, condensing and refluxing conditions. The resulting emulsion was centrifuged for 5min (8000 r/min), washed with absolute ethanol and dried (60 ℃ C., 12 h) to give a white product B.
Step (3): 0.6g of product B was dispersed in 200mL of absolute ethanol, 16mL of hydrochloric acid (12M) was added to remove excess CTAB, transferred to a three-necked flask, placed in an oil bath and maintained at 70℃for 24h under stirring, condensing and refluxing conditions. Centrifuging the obtained emulsion solution for 5min (8000 r/min), washing and drying with absolute ethyl alcohol (60 ℃ for 12 h) to obtain the white product dendritic fiber-shaped nano silicon Dioxide (DFNS).
Step (4): 0.6g of DFNS is dispersed into a beaker filled with 240mL of deionized water, 2.4g of polyvinylpyrrolidone (PVP) with a molecular weight of 40000 is added as a surface modifier, the mixture is stirred for 12 hours to obtain a turbid solution, the obtained turbid solution is subjected to centrifugation (8000 r/min) for 5 minutes, and the obtained turbid solution is washed and dried by absolute ethyl alcohol (60 ℃ for 12 hours) to obtain white product PVP dispersed DFNS (P-DFNS).
In the step (5), 0.3-g P-DFNS is dispersed in 180mL of water, stirred and dispersed evenly by ultrasonic, 0.21g of resorcinol and 0.3mL of formaldehyde solution (37%) are added, then 0.42mL of ammonia water is added, and 0.21mL of TEOS is added dropwise. The mixed solution is placed in an oil bath pot and stirred for 2 hours at 50 ℃ to obtain a brown solution, the obtained turbid solution is centrifuged (8000 r/min), and the turbid solution is washed and dried by absolute ethyl alcohol (60 ℃ for 12 hours) to obtain a phenolic resin coated P-DFNS brown product (P-DFNS@RF).
And (6) loading the P-DFNS@RF into a corundum porcelain boat, placing the corundum porcelain boat into a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon, preserving heat for 4 hours, naturally cooling to room temperature, and annealing to carbonize the phenolic resin to obtain a black product (P-DFNS@C).
And (7) dispersing the P-DFNS@C into an excessive HF solution (10wt%) for etching to remove the P-DFNS (24 h), and carrying out suction filtration and drying to obtain the hollow mesoporous carbon spheres (IW-MHCS 0.21/0.21) with wrinkles on the inner surface of the black product.
The negative electrode plate of the potassium ion battery is prepared by 80% of hollow mesoporous carbon sphere (IW-MHCS 0.21/0.21) powder with wrinkled inner surface, 10% of acetylene black and 10% of binder by mass percent, and the metallic potassium plate is adopted as the positive electrode of a half battery. And testing the electrochemical performance of the hollow mesoporous carbon sphere electrode material with the wrinkled inner surface by adopting a blue electric testing system and an electrochemical workstation, wherein the voltage range is 0.01-3.0V.
FIGS. 1-4 are pictures obtained by characterization and electrochemical testing of the inner surface crimped hollow mesoporous carbon sphere (IW-MHCS 0.21/0.21) powder obtained in example 1. Wherein: FIG. 1 is an SEM image of the inner surface crimped hollow mesoporous carbon sphere (IW-MHCS 0.21/0.21) powder. FIG. 2 is an XRD pattern of the inner surface crimped hollow mesoporous carbon sphere (IW-MHCS 0.21/0.21) powder. FIG. 3 is a graph of the particle size distribution of the inner surface crimped hollow mesoporous carbon sphere (IW-MHCS 0.21/0.21) powder. FIG. 4 is a cycle chart of an inner surface corrugated hollow mesoporous carbon sphere (IW-MHCS 0.21/0.21) as a negative electrode material for a potassium ion battery at a current density of 1000 mA/g. The electrochemical performance test of the battery adopts a voltage of 0.01-3.0V, and the reversible capacity is maintained at 203.7mAh/g after 500 cycles under the current density of 1000mA/g through detection.
Example 2
The IW-MHCS 0.255/0.255 inner surface corrugated hollow mesoporous carbon sphere potassium ion battery cathode material is compounded by the modes of coprecipitation, polycondensation, modification, heat treatment, etching and washing filtration of raw materials.
The preparation method of the hollow mesoporous carbon sphere with the wrinkled inner surface comprises the following steps of:
step (1): cetyl trimethylammonium bromide (CTAB) (2.0 g), urea (1.2 g), isopropyl alcohol (1.84 mL), cyclohexane (60 mL) and deionized water (60 mL) were mixed in a three-necked flask and stirred at room temperature for 4 hours to give a solution A.
Step (2): tetraethyl silicate (TEOS) (6.0 mL) was added dropwise to solution a and placed in an oil bath for 16h at 70 ℃ under stirring, condensing and refluxing conditions. The resulting emulsion was centrifuged for 5min (8000 r/min), washed with absolute ethanol and dried (60 ℃ C., 12 h) to give a white product B.
Step (3): 0.6g of product B was dispersed in 200mL of absolute ethanol, 16mL of hydrochloric acid (12M) was added to remove excess CTAB, transferred to a three-necked flask, placed in an oil bath and maintained at 70℃for 24h under stirring, condensing and refluxing conditions. Centrifuging the obtained emulsion solution for 5min (8000 r/min), washing and drying with absolute ethyl alcohol (60 ℃ for 12 h) to obtain the white product dendritic fiber-shaped nano silicon Dioxide (DFNS).
Step (4): 0.6g of DFNS is dispersed into a beaker filled with 240mL of deionized water, 2.4g of polyvinylpyrrolidone (PVP) with a molecular weight of 40000 is added as a surface modifier, the mixture is stirred for 12 hours to obtain a turbid solution, the obtained turbid solution is subjected to centrifugation (8000 r/min) for 5 minutes, and the obtained turbid solution is washed and dried by absolute ethyl alcohol (60 ℃ for 12 hours) to obtain white product PVP dispersed DFNS (P-DFNS).
In the step (5), 0.3-g P-DFNS is dispersed in 180mL of water, stirred and dispersed evenly by ultrasonic, 0.255g of resorcinol and 0.42mL of formaldehyde solution (37%) are added, then 0.42mL of ammonia water is added, and 0.255mL of TEOS is added dropwise. The mixed solution is placed in an oil bath pot and stirred for 2 hours at 50 ℃ to obtain a brown solution, the obtained turbid solution is centrifuged for 5 minutes (8000 r/min), and the turbid solution is washed and dried by absolute ethyl alcohol (60 ℃ for 12 hours) to obtain a phenolic resin coated P-DFNS brown product (P-DFNS@RF).
And (6) loading the P-DFNS@RF into a corundum porcelain boat, placing the corundum porcelain boat into a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon, preserving heat for 4 hours, naturally cooling to room temperature, and annealing to carbonize the phenolic resin to obtain a black product (P-DFNS@C).
And (7) dispersing the P-DFNS@C into an excessive HF solution (10wt%) for etching to remove the P-DFNS (24 h), and carrying out suction filtration and drying to obtain the hollow mesoporous carbon spheres (IW-MHCS 0.255/0.255) with wrinkles on the inner surface of the black product.
The negative electrode plate of the potassium ion battery is prepared from 10% of acetylene black and 10% of binder by mass percent by using the hollow mesoporous carbon sphere (IW-MHCS 0.255/0.255) powder with the wrinkled inner surface, and the metallic potassium plate is adopted as the positive electrode of the half battery. And testing the electrochemical performance of the hollow mesoporous carbon sphere electrode material with the wrinkled inner surface by adopting a blue electric testing system and an electrochemical workstation, wherein the voltage range is 0.01-3.0V.
Fig. 5-7 are pictures obtained by characterization and electrochemical testing of the inner surface crimped hollow mesoporous carbon sphere (IW-mhc s 0.255/0.255) powder obtained in example 2. Wherein: FIG. 5 is an SEM image of the inner surface crimped hollow mesoporous carbon sphere (IW-MHCS 0.255/0.255) powder. FIG. 6 is a graph of the particle size distribution of the inner surface crimped hollow mesoporous carbon sphere (IW-MHCS 0.255/0.255) powder. FIG. 7 is a cycle chart of an inner surface corrugated hollow mesoporous carbon sphere (IW-MHCS 0.255/0.255) as a negative electrode material for a potassium ion battery at a current density of 1000 mA/g. The electrochemical performance test of the battery adopts a voltage of 0.01-3.0V, and the reversible capacity is kept at 166mAh/g after 500 cycles under a current density of 1000mA/g through detection.
Example 3
The IW-MHCS 0.3/0.3 inner surface corrugated hollow mesoporous carbon sphere potassium ion battery cathode material is compounded by the modes of coprecipitation, polycondensation, modification, heat treatment, etching and washing filtration of raw materials.
The preparation method of the hollow mesoporous carbon sphere with the wrinkled inner surface comprises the following steps of:
step (1): cetyl trimethylammonium bromide (CTAB) (2.0 g), urea (1.2 g), isopropyl alcohol (1.84 mL), cyclohexane (60 mL) and deionized water (60 mL) were mixed in a three-necked flask and stirred at room temperature for 4 hours to give a solution A.
Step (2): tetraethyl silicate (TEOS) (6.0 mL) was added dropwise to solution a and placed in an oil bath for 16h at 70 ℃ under stirring, condensing and refluxing conditions. The resulting emulsion was centrifuged for 5min (8000 r/min), washed with absolute ethanol and dried (60 ℃ C., 12 h) to give a white product B.
Step (3): 0.6g of product B was dispersed in 200mL of absolute ethanol, 16mL of hydrochloric acid (12M) was added to remove excess CTAB, transferred to a three-necked flask, placed in an oil bath and maintained at 70℃for 24h under stirring, condensing and refluxing conditions. Centrifuging the obtained emulsion solution for 5min (8000 r/min), washing and drying with absolute ethyl alcohol (60 ℃ for 12 h) to obtain the white product dendritic fiber-shaped nano silicon Dioxide (DFNS).
Step (4): 0.6g of DFNS is dispersed into a beaker filled with 240mL of deionized water, 2.4g of polyvinylpyrrolidone (PVP) with a molecular weight of 40000 is added as a surface modifier, the mixture is stirred for 12 hours to obtain a turbid solution, the obtained turbid solution is subjected to centrifugation (8000 r/min) for 5 minutes, and the obtained turbid solution is washed and dried by absolute ethyl alcohol (60 ℃ for 12 hours) to obtain white product PVP dispersed DFNS (P-DFNS).
In the step (5), 0.3-g P-DFNS is dispersed in 180mL of water, stirred and dispersed evenly by ultrasonic, 0.3g of resorcinol and 0.42mL of formaldehyde solution (37%) are added, then 0.42mL of ammonia water is added, and 0.3mL of TEOS is added dropwise. The mixed solution is placed in an oil bath pot and stirred for 2 hours at 50 ℃ to obtain a brown solution, the obtained turbid solution is centrifuged for 5 minutes (8000 r/min), and the turbid solution is washed and dried by absolute ethyl alcohol (60 ℃ for 12 hours) to obtain a phenolic resin coated P-DFNS brown product (P-DFNS@RF).
And (6) loading the P-DFNS@RF into a corundum porcelain boat, placing the corundum porcelain boat into a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under the atmosphere of argon, preserving heat for 4 hours, naturally cooling to room temperature, and annealing to carbonize the phenolic resin to obtain a black product (P-DFNS@C).
And (7) dispersing the P-DFNS@C into an excessive HF solution (10wt%) for etching to remove the P-DFNS (24 h), and carrying out suction filtration and drying to obtain the hollow mesoporous carbon spheres (IW-MHCS 0.3/0.3) with wrinkles on the inner surface of the black product.
The negative electrode plate of the potassium ion battery is prepared by 80% of hollow mesoporous carbon sphere (IW-MHCS 0.3/0.3) powder with wrinkled inner surface, 10% of acetylene black and 10% of binder by mass percent, and the metallic potassium plate is adopted as the positive electrode of a half battery. And testing the electrochemical performance of the hollow mesoporous carbon sphere electrode material with the wrinkled inner surface by adopting a blue electric testing system and an electrochemical workstation, wherein the voltage range is 0.01-3.0V.
Fig. 8-10 are pictures obtained by characterization and electrochemical testing of the inner surface crimped hollow mesoporous carbon sphere (IW-mhc s 0.3/0.3) powder obtained in example 3. Wherein: FIG. 8 is an SEM image of the inner surface crimped hollow mesoporous carbon sphere (IW-MHCS 0.3/0.3) powder. FIG. 9 is a graph of the particle size distribution of the inner surface crimped hollow mesoporous carbon sphere (IW-MHCS 0.3/0.3) powder. FIG. 10 is a cycle chart of an inner surface corrugated hollow mesoporous carbon sphere (IW-MHCS 0.3/0.3) as a negative electrode material for a potassium ion battery at a current density of 1000 mA/g. The electrochemical performance test of the battery adopts a voltage of 0.01-3.0V, and the reversible capacity is kept at 129.9mAh/g after 500 cycles under a current density of 1000mA/g through detection.
According to examples 1, 2 and 3, it can be seen from SEM images that the coating condition of the carbon sphere changes with the coating amount of the phenolic resin, the thickness of the shell layer of the carbon sphere becomes thicker with the increase of the coating amount, the overall morphology of the carbon sphere becomes complete and uniform gradually, and the average particle size of three samples becomes larger with the increase of the coating amount, which proves that the coating amount of the phenolic resin has a significant influence on the morphology of the carbon sphere.
Example 4 (comparative example)
The hollow mesoporous carbon sphere potassium ion battery cathode material with the inner surface of the IW-MHCS is compounded by modes of coprecipitation, polycondensation, modification, heat treatment, etching, washing and filtering of raw materials. PVP modification is carried out on the DFNS sacrificial template, and finally three carbon sphere materials with different coating conditions are obtained.
The preparation method of the hollow mesoporous carbon sphere with the wrinkled inner surface comprises the following steps of:
step (1): cetyl trimethylammonium bromide (CTAB) (2.0 g), urea (1.2 g), isopropyl alcohol (1.84 mL), cyclohexane (60 mL) and deionized water (60 mL) were mixed in a three-necked flask and stirred at room temperature for 4 hours to give a solution A.
Step (2): tetraethyl silicate (TEOS) (6.0 mL) was added dropwise to solution a and placed in an oil bath for 16h at 70 ℃ under stirring, condensing and refluxing conditions. The resulting emulsion was centrifuged for 5min (8000 r/min), washed with absolute ethanol and dried (60 ℃ C., 12 h) to give a white product B.
Step (3): 0.6g of product B was dispersed in 200mL of absolute ethanol, 16mL of hydrochloric acid (12M) was added to remove excess CTAB, transferred to a three-necked flask, placed in an oil bath and maintained at 70℃for 24h under stirring, condensing and refluxing conditions. Centrifuging the obtained emulsion solution for 5min (8000 r/min), washing and drying with absolute ethyl alcohol (60 ℃ for 12 h) to obtain the white product dendritic fiber-shaped nano silicon Dioxide (DFNS).
Step (4): 0.3g of DFNS was dispersed in 180mL of water, stirred with ultrasound uniformly, 0.3g of resorcinol and 0.42mL of formaldehyde solution (37%) were added, followed by 0.42mL of ammonia, and 0.3mL of TEOS was added dropwise. The mixed solution is placed in an oil bath pot and stirred for 2 hours at 50 ℃ to obtain brown solution, the obtained turbid solution is centrifuged for 5 minutes (8000 r/min), and the turbid solution is washed and dried by absolute ethyl alcohol (60 ℃ and 12 hours) to obtain phenolic resin coated P-DFNS brown products (0-DFNS@RF).
And (5) loading the P-DFNS@RF sample obtained in the step (4) into a corundum porcelain boat, placing the corundum porcelain boat into a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, preserving heat for 4 hours, naturally cooling to room temperature, and annealing to carbonize the phenolic resin to obtain a black product (0-DFNS@C).
And (7) dispersing the P-DFNS@C into an excessive HF solution (10wt%) for etching to remove the P-DFNS (24 h), and carrying out suction filtration and drying to obtain the hollow mesoporous carbon spheres (0-IW-MHCS) with folds on the inner surface of the black product.
The negative electrode plate of the potassium ion battery is prepared by 80% of the hollow mesoporous carbon sphere (0-IW-MHCS) powder with the wrinkled inner surface, 10% of acetylene black and 10% of adhesive in percentage by mass, and the metal potassium plate is adopted as the positive electrode of the half battery. And testing the electrochemical performance of the hollow mesoporous carbon sphere electrode material with the wrinkled inner surface by adopting a blue electric testing system and an electrochemical workstation, wherein the voltage range is 0.01-3.0V.
Fig. 11 and 12 are pictures obtained by characterizing and electrochemically testing the hollow mesoporous carbon sphere (0-IW-mhc) powder with the inner surface crimped as obtained in example 4. Wherein: FIG. 11 is an SEM image of a hollow mesoporous carbon sphere (0-IW-MHCS) powder with internal surface folds prepared using a sacrificial template that was not PVP treated. FIG. 12 is a cycle chart of an inner surface corrugated hollow mesoporous carbon sphere (0-IW-MHCS) prepared using a sacrificial template without PVP treatment as a negative electrode material for a potassium ion battery at a current density of 1000 mA/g. The electrochemical performance test of the battery adopts a voltage of 0.01-3.0V, and the reversible capacity is kept at 114.7mAh/g after 500 cycles under the current density of 1000mA/g through detection.
Example 5
The hollow mesoporous carbon sphere potassium ion battery cathode material with the inner surface of the IW-MHCS is compounded by modes of coprecipitation, polycondensation, modification, heat treatment, etching, washing and filtering of raw materials. PVP modification is carried out on the DFNS sacrificial template, and finally three carbon sphere materials with different coating conditions are obtained.
The preparation method of the hollow mesoporous carbon sphere with the wrinkled inner surface comprises the following steps of:
step (1): cetyl trimethylammonium bromide (CTAB) (2.0 g), urea (1.2 g), isopropyl alcohol (1.84 mL), cyclohexane (60 mL) and deionized water (60 mL) were mixed in a three-necked flask and stirred at room temperature for 4 hours to give a solution A.
Step (2): tetraethyl silicate (TEOS) (6.0 mL) was added dropwise to solution a and placed in an oil bath for 16h at 70 ℃ under stirring, condensing and refluxing conditions. The resulting emulsion was centrifuged for 5min (8000 r/min), washed with absolute ethanol and dried (60 ℃ C., 12 h) to give a white product B.
Step (3): 0.6g of product B was dispersed in 200mL of absolute ethanol, 16mL of hydrochloric acid (12M) was added to remove excess CTAB, transferred to a three-necked flask, placed in an oil bath and maintained at 70℃for 24h under stirring, condensing and refluxing conditions. Centrifuging the obtained emulsion solution for 5min (8000 r/min), washing and drying with absolute ethyl alcohol (60 ℃ for 12 h) to obtain the white product dendritic fiber-shaped nano silicon Dioxide (DFNS).
Step (4): the DFNS samples obtained according to the procedure described above were subjected to a 58000 molecular weight PVP treatment in this step. Dispersing 0.6g of DFNS into a beaker filled with 240mL of deionized water respectively, adding 2.4g of polyvinylpyrrolidone (PVP) with a molecular weight of 58000 as a surface modifier respectively, stirring for 12h to obtain a turbid solution, centrifuging the obtained turbid solution for 5min (8000 r/min), washing and drying with absolute ethyl alcohol (60 ℃ for 12 h) to obtain white product PVP dispersed DFNS (P-DFNS, P is 58000).
In the step (5), 0.3g P-DFNS (58000-DFNS) is dispersed in 180mL of water, stirred and dispersed evenly by ultrasonic, 0.3g of resorcinol and 0.42mL of formaldehyde solution (37%) are added, then 0.42mL of ammonia water is added, and 0.3mL of TEOS is added dropwise. The mixed solution is placed in an oil bath pot and stirred for 2 hours at 50 ℃ to obtain a brown solution, the obtained turbid solution is centrifuged for 5 minutes (8000 r/min), and the turbid solution is washed and dried by absolute ethyl alcohol (60 ℃ for 12 hours) to obtain a phenolic resin coated P-DFNS brown product (58000-DFNS@RF).
And (6) loading the three P-DFNS@RF samples obtained in the step (5) into a corundum porcelain boat, placing the corundum porcelain boat into a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, preserving heat for 4 hours, naturally cooling to room temperature, and annealing to carbonize the phenolic resin to obtain a black product (58000-DFNS@C).
And (7) dispersing the P-DFNS@C into an excessive HF solution (10wt%) for etching to remove the P-DFNS (24 h), and carrying out suction filtration and drying to obtain the hollow mesoporous carbon spheres (58000-IW-MHCS) with folds on the inner surface of the black product.
Fig. 13 and 14 are pictures obtained by characterizing and electrochemically testing the hollow mesoporous carbon sphere (58000-IW-mhc) powder with the inner surface crimped as obtained in example 5. Wherein: FIG. 13 is an SEM image of an inner surface crimped hollow mesoporous carbon sphere (58000-IW-MHCS) powder prepared using a 58000 molecular weight PVP treated sacrificial template. FIG. 14 is a cycle chart of an inner surface corrugated hollow mesoporous carbon sphere (58000-IW-MHCS) prepared using a 58000 molecular weight PVP treated sacrificial template as a negative electrode material for a potassium ion battery at a current density of 1000 mA/g. The electrochemical performance test of the battery adopts a voltage of 0.01-3.0V, and the reversible capacity is kept at 124.8mAh/g after 500 cycles under the current density of 1000mA/g through detection.
According to examples 3, 4 and 5 above, it can be seen from SEM images that the coating of the carbon spheres changed with PVP treatment. In the three examples, the hollow mesoporous carbon spheres with the wrinkles on the inner surface prepared by using the sacrificial template treated by 40000 molecular weight PVP have the most uniform coating morphology, and the best electrochemical performance is achieved.
Example 6
The hollow mesoporous carbon sphere potassium ion battery cathode material with the inner surface of the IW-MHCS is compounded by modes of coprecipitation, polycondensation, modification, heat treatment, etching, washing and filtering of raw materials. And finally, three carbon sphere materials with different morphologies are obtained by regulating and controlling synthesis conditions of the DFNS sacrificial template.
The preparation method of the hollow mesoporous carbon sphere with the wrinkled inner surface comprises the following steps of:
step (1): two sets of DFNS samples of different volume ratios of cyclohexane and deionized water were designed. A mixed solution of cetyltrimethylammonium bromide (CTAB) (2.0 g), urea (1.2 g), isopropyl alcohol (1.84 mL), cyclohexane (50 mL) and deionized water (70 mL) having a purity of analytical purity was taken and mixed in a three-necked flask, and stirred at room temperature for 4 hours to obtain a solution A.
Step (2): tetraethyl silicate (TEOS) (6.0 mL) was added dropwise to the solution a and placed in an oil bath for 16h at 70 ℃ under stirring, condensing and refluxing conditions. The resulting emulsion was centrifuged for 5min (8000 r/min), washed with absolute ethanol and dried (60 ℃ C., 12 h) to give a white product B.
Step (3): 0.6g of product B was dispersed in a three-necked flask containing 200mL of absolute ethanol, 16mL of hydrochloric acid (12M) was added to remove excess CTAB, placed in an oil bath and maintained at 70℃for 24h under reflux with stirring and condensation. Centrifuging the obtained emulsion solution for 5min (8000 r/min), washing and drying with absolute ethyl alcohol (60 ℃ for 12 h) to obtain the white product dendritic fiber-shaped nano silicon dioxide, wherein the water-oil ratio is named as DFNS 7/5.
Step (4): 0.6g of DFNS is dispersed into a beaker filled with 240mL of deionized water, 2.4g of polyvinylpyrrolidone (PVP) with a molecular weight of 40000 is added as a surface modifier, the mixture is stirred for 12 hours to obtain a turbid solution, the obtained turbid solution is centrifuged for 5 minutes (8000 r/min), and the obtained turbid solution is washed and dried by absolute ethyl alcohol (60 ℃ for 12 hours) to obtain white product PVP dispersed DFNS (P-DFNS 7/5).
In the step (5), 0.3g of DFNS 7/5 is dispersed in 180mL of water, stirred and dispersed evenly by ultrasonic, 0.3g of resorcinol and 0.42mL of formaldehyde solution (37%) are added respectively, then 0.42mL of ammonia water is added, and 0.3mL of TEOS is added dropwise. The mixed solution is placed in an oil bath pot and stirred for 2 hours at 50 ℃ to obtain a brown solution, the obtained turbid solution is centrifuged for 5 minutes (8000 r/min), and the turbid solution is washed and dried by absolute ethyl alcohol (60 ℃ for 12 hours) to obtain a phenolic resin coated P-DFNS brown product (P-DFNS@RF 7/5).
And (6) loading the DFNS@RF sample obtained in the step (5) into a corundum porcelain boat, placing the corundum porcelain boat into a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, preserving heat for 4 hours, naturally cooling to room temperature, and annealing to carbonize the phenolic resin to obtain a black product (P-DFNS@C7/5).
And (7) dispersing the P-DFNS@C7/5 into an excessive HF solution (10wt%) for etching to remove the P-DFNS (24 h), and carrying out suction filtration and drying to obtain the hollow mesoporous carbon spheres (C7/5) with the inner surface wrinkled black products.
The negative electrode plate of the potassium ion battery is prepared by 80% of the hollow mesoporous carbon sphere (C7/5) powder with the wrinkled inner surface, 10% of acetylene black and 10% of binder by mass percent, and the metallic potassium plate is adopted as the positive electrode of the half battery. And testing the electrochemical performance of the hollow mesoporous carbon sphere electrode material with the wrinkled inner surface by adopting a blue electric testing system and an electrochemical workstation, wherein the voltage range is 0.01-3.0V.
FIGS. 15-20 are pictures obtained by characterization testing of three inner surface crimped hollow mesoporous carbon sphere (C7/5) powders obtained in example 6. Wherein: FIG. 15 (a) is an SEM image of DFNS 7/5 powder. FIG. 16 is a BET spectrum of DFNS 7/5. FIG. 17 is a BJH pattern of DFNS 7/5. FIG. 18 is a BET spectrum of the hollow mesoporous carbon sphere (C7/5) powder with the inner surface wrinkled. FIG. 19 is a BJH spectrum of the hollow mesoporous carbon sphere (C7/5) powder with the inner surface wrinkled. FIG. 20 is a cycle chart of the hollow mesoporous carbon sphere (C7/5) with the inner surface wrinkled prepared in example 6 as a cathode material of a potassium ion battery at a current density of 1000 mA/g. The electrochemical performance test of the battery adopts a voltage of 0.01-3.0V, and the reversible capacity is kept at 122.5mAh/g after 500 cycles under the current density of 1000mA/g through detection.
Example 7
The hollow mesoporous carbon sphere potassium ion battery cathode material with the inner surface of the IW-MHCS is compounded by modes of coprecipitation, polycondensation, modification, heat treatment, etching, washing and filtering of raw materials. And finally, three carbon sphere materials with different morphologies are obtained by regulating and controlling synthesis conditions of the DFNS sacrificial template.
The preparation method of the hollow mesoporous carbon sphere with the wrinkled inner surface comprises the following steps of:
step (1): two sets of DFNS samples of different volume ratios of cyclohexane and deionized water were designed. A mixed solution of cetyltrimethylammonium bromide (CTAB) (2.0 g), urea (1.2 g), isopropyl alcohol (1.84 mL), cyclohexane (70 mL) and deionized water (50 mL) having a purity of analytical purity was taken and mixed in a three-necked flask, and stirred at room temperature for 4 hours to obtain a solution A.
Step (2): tetraethyl silicate (TEOS) (6.0 mL) was added dropwise to the solution a and placed in an oil bath for 16h at 70 ℃ under stirring, condensing and refluxing conditions. The resulting emulsion was centrifuged for 5min (8000 r/min), washed with absolute ethanol and dried (60 ℃ C., 12 h) to give a white product B.
Step (3): 0.6g of product B was dispersed in a three-necked flask containing 200mL of absolute ethanol, 16mL of hydrochloric acid (12M) was added to remove excess CTAB, placed in an oil bath and maintained at 70℃for 24h under reflux with stirring and condensation. The obtained emulsion solution is centrifuged for 5min (8000 r/min), and is washed and dried by absolute ethyl alcohol (60 ℃ C., 12 h) to obtain the white product dendritic fiber-shaped nano silicon dioxide, which is named as DFNS 5/7 due to the water-oil ratio.
Step (4): 0.6g of DFNS is dispersed into a beaker filled with 240mL of deionized water, 2.4g of polyvinylpyrrolidone (PVP) with a molecular weight of 40000 is added as a surface modifier, the mixture is stirred for 12 hours to obtain a turbid solution, the obtained turbid solution is centrifuged for 5 minutes (8000 r/min), and the obtained turbid solution is washed and dried by absolute ethyl alcohol (60 ℃ for 12 hours) to obtain white product PVP dispersed DFNS (P-DFNS 5/7).
In the step (5), 0.3g of P-DFNS 5/7 is dispersed in 180mL of water, stirred and dispersed evenly by ultrasonic, 0.3g of resorcinol and 0.42mL of formaldehyde solution (37%) are added respectively, then 0.42mL of ammonia water is added, and 0.3mL of TEOS is added dropwise. The mixed solution is placed in an oil bath pot and stirred for 2 hours at 50 ℃ to obtain a brown solution, the obtained turbid solution is centrifuged for 5 minutes (8000 r/min), and the turbid solution is washed and dried by absolute ethyl alcohol (60 ℃ for 12 hours) to obtain a phenolic resin coated P-DFNS brown product (P-DFNS@RF 5/7).
And (6) loading the DFNS@RF sample obtained in the step (5) into a corundum porcelain boat, placing the corundum porcelain boat into a tube furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, preserving heat for 4 hours, naturally cooling to room temperature, and annealing to carbonize the phenolic resin to obtain a black product (P-DFNS@C5/7).
And (7) dispersing the P-DFNS@C5/7 into an excessive HF solution (10wt%) for etching to remove the P-DFNS (24 h), and carrying out suction filtration and drying to obtain the hollow mesoporous carbon spheres (C5/7) with the inner surface wrinkled black products.
The negative electrode plate of the potassium ion battery is prepared by 80% of the hollow mesoporous carbon sphere (C7/5) powder with the wrinkled inner surface, 10% of acetylene black and 10% of binder by mass percent, and the metallic potassium plate is adopted as the positive electrode of the half battery. And testing the electrochemical performance of the hollow mesoporous carbon sphere electrode material with the wrinkled inner surface by adopting a blue electric testing system and an electrochemical workstation, wherein the voltage range is 0.01-3.0V.
FIGS. 15, 21-25 are pictures obtained by characterization testing of three inner surface crimped hollow mesoporous carbon spheres (C7/5) powders obtained in example 7. Wherein: FIG. 15 (C) is an SEM image of DFNS 5/7 powder. FIG. 21 is a BET spectrum of DFNS 5/7. FIG. 22 is a BJH pattern of DFNS 5/7. FIG. 23 is a BET spectrum of the hollow mesoporous carbon sphere (C5/7) powder with the inner surface wrinkled. FIG. 24 is a BJH spectrum of the hollow mesoporous carbon sphere (C5/7) powder with the inner surface wrinkled. FIG. 25 is a cycle chart of the hollow mesoporous carbon sphere (C5/7) with the inner surface wrinkled prepared in example 7 as a cathode material of a potassium ion battery at a current density of 1000 mA/g. The electrochemical performance test of the battery adopts a voltage of 0.01-3.0V, and the reversible capacity is kept at 117.5mAh/g after 500 cycles under the current density of 1000mA/g through detection.
According to the above examples 3, 6 and 7, fig. 15 (b) is an SEM image of the DFNS powder of example 3, and it can be seen from the SEM image of fig. 15 that the morphology of the DFNS sacrificial template changes with the change of the water-oil ratio, the specific surface area of the sacrificial template of the prepared DFNS gradually decreases and the pore size gradually increases as the water-oil ratio decreases, and the specific surface area of the hollow mesoporous carbon sphere of the corresponding prepared inner surface fold gradually increases. Three examples were combined and compared using a water to oil ratio of 1:1, the hollow mesoporous carbon sphere with the inner surface wrinkled, which is obtained by taking the DFNS prepared by 1 as a sacrificial template, has the optimal electrochemical performance.
The embodiment can be seen from an electrochemical performance test chart, and the hollow mesoporous carbon sphere electrode material with the wrinkled inner surface has very high specific capacity, excellent cycle stability and excellent rate performance. Wherein the reversible capacity of the electrode material prepared in the embodiment 1 after 500 cycles under the current density of 1000mA/g is as high as 203.7mAh/g, which fully represents the performance advantage of the carbon-based negative electrode material. The preparation method provided by the invention has the advantages of simple process and strong operability, and is suitable for industrial production. The application and popularization of the high-capacity electrode material have positive promotion effects on promoting the preparation and application of the high-capacity electrode material. Therefore, the invention has important social value and economic value.
The technical scheme of the invention is explained in the technical scheme, the protection scope of the invention cannot be limited by the technical scheme, and any changes and modifications to the technical scheme according to the technical substance of the invention belong to the protection scope of the technical scheme of the invention.
Claims (9)
1. A preparation method of hollow mesoporous carbon spheres with folds on the inner surface is characterized by comprising the following steps of: adopts dendritic fiber-shaped nano SiO 2 (DFNS) as sacrificial template, aggregatedAfter the vinyl pyrrolidone is modified, coating with phenolic resin, adding tetraethyl silicate to introduce mesopores, annealing, and removing a sacrificial template by hydrofluoric acid etching to obtain hollow mesoporous carbon spheres (IW-MHCS) with folds on the inner surface; the preparation method comprises the following steps:
step (1): dissolving CTAB, isopropanol and urea in a mixed solution of cyclohexane and water to obtain a solution A;
step (2): dropwise adding tetraethyl silicate into the solution A, and reacting at 60-80 ℃ for 12-20h to obtain a white product B;
step (3): dispersing the white product B in absolute ethyl alcohol, adding hydrochloric acid to remove residual CTAB, and reacting at 60-80 ℃ for 18-30h to obtain dendritic fiber-shaped nano SiO 2 (DFNS)；
Step (4): dispersing DFNS as a sacrificial template into water, adding PVP surface modifier to obtain white product PVP dispersed DFNS, namely P-DFNS;
dispersing the P-DFNS in water, adding resorcinol and formaldehyde, then adding ammonia water, then dropwise adding TEOS, and reacting for 2-4 hours at 50-80 ℃ to obtain a phenolic resin coated P-DFNS brown product which is marked as P-DFNS@RF;
annealing the P-DFNS@RF under a protective atmosphere to carbonize the phenolic resin to obtain a black product, which is marked as P-DFNS@C;
dispersing P-DFNS@C into HF solution, etching to remove P-DFNS, filtering, and oven drying to obtain black product IW-MHCS with carbon layer thickness of 10-50nm, particle diameter of 400-600nm, smooth outer surface, corrugated inner surface, mesoporous distributed on the carbon layer surface, mesoporous diameter of 3-20nm, and specific surface area of 400-700m 2 /g。
2. The method for preparing the hollow mesoporous carbon sphere with the wrinkled inner surface according to claim 1, wherein the method comprises the following steps: the preparation method comprises the following specific steps of:
step (1): taking 1-3.0g of CTAB as a surfactant, 1-3ml of isopropanol as a cosurfactant and urea with the mass ratio of 0.6:1 with CTAB, dissolving in 120-150ml of cyclohexane and water mixed solution, and stirring uniformly at room temperature to obtain solution A; wherein the volume ratio of cyclohexane to water is (5-7): (5-7);
Step (2): adding tetraethyl silicate into the solution A dropwise in an amount of 1/20 of the volume of the solution A, and reacting for 12-20h at 60-80 ℃; centrifuging the obtained emulsion solution, washing and drying to obtain a white product B;
step (3): dispersing 0.3-1g of white product B in 200-300mL of absolute ethyl alcohol, adding 15-20mL of hydrochloric acid to remove residual CTAB, reacting at 60-80 ℃ for 18-30h, centrifuging the obtained emulsion solution, washing and drying to obtain DFNS;
step (4): dispersing 0.5-1g of DFNS serving as a sacrificial template into 240-300ml of water, adding 2-3g of PVP surface modifier, stirring to obtain a turbid solution, centrifuging, washing and drying to obtain white product PVP dispersed DFNS, namely P-DFNS;
dispersing 0.3-0.6-g P-DFNS in 180-360ml of water, stirring and dispersing uniformly by ultrasonic, adding 0.15-0.75g of resorcinol and 0.21-1.05ml of formaldehyde solution, then adding 400-500 mu l of ammonia water, and then dropwise adding TEOS, wherein the mass volume ratio g of resorcinol to TEOS is (1-3); reacting the mixed solution at 50-80 ℃ for 2-4 hours to obtain a brown turbid solution, and performing centrifugal separation, washing and drying to obtain a phenolic resin coated P-DFNS brown product, which is marked as P-DFNS@RF;
Annealing the P-DFNS@RF in a protective atmosphere at 600-1000 ℃, and preserving heat for 2-6 hours to carbonize the phenolic resin to obtain a black product, which is denoted as P-DFNS@C;
and (7) dispersing the P-DFNS@C into an HF solution, etching to remove the P-DFNS, and carrying out suction filtration and drying to obtain a black product IW-MHCS.
3. The method for preparing the hollow mesoporous carbon sphere with the wrinkled inner surface according to claim 2, wherein the method comprises the following steps: in the steps (2), (3), (4) and (5), the drying temperature is 50-80 ℃ and the drying time is 10-20h.
4. The method for preparing the hollow mesoporous carbon sphere with the wrinkled inner surface according to claim 2, wherein the method comprises the following steps: in the step (4), the molecular weight of PVP ranges from 8000 to 200000.
5. The method for preparing the hollow mesoporous carbon sphere with the wrinkled inner surface according to claim 2, wherein the method comprises the following steps: further, in the step (5), the mass concentration of the formaldehyde solution is 37%, and the mass concentration of the ammonia water is 25-28%; in the step (6), the annealing heating rate is 2-8 ℃/min.
6. The method for preparing the hollow mesoporous carbon sphere with the wrinkled inner surface according to claim 2, wherein the method comprises the following steps: in the step (7), the concentration of the HF solution is 10-30wt% and the etching time is 4-24h.
7. The method for preparing the hollow mesoporous carbon sphere with the wrinkled inner surface according to claim 2, wherein the method comprises the following steps: in the step (7), the hollow mesoporous carbon spheres with the inner surface wrinkled are in a powder state and have a spherical appearance.
8. Use of hollow mesoporous carbon spheres prepared by the preparation method according to any one of claims 1 to 7 as a negative electrode material of a potassium ion battery.
9. The use of the hollow mesoporous carbon sphere as a negative electrode material of a potassium ion battery according to claim 8, wherein: the method comprises the following specific steps:
(1) According to the mass percentage of each component, 70-80% of hollow mesoporous carbon spheres with wrinkles on the inner surface, 10-15% of acetylene black and 10-15% of binder are mixed and magnetically stirred for 2-4 hours to obtain slurry;
(2) Coating the slurry on the surface of a copper foil, wherein the coating thickness is 100-150 mu m, and vacuum drying to prepare a potassium ion battery negative plate;
(3) The metal potassium sheet is used as a battery positive plate, the battery is assembled, and the electrochemical performance of the battery is tested;
in the step (3), the voltage adopted for testing the electrochemical performance of the battery is 0.01-3.0V, and after detection, the reversible capacity is kept between 110 mAh/g and 350mAh/g after 500 cycles under the current density of 1000 mA/g.
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