CN115084483A - Walnut shell derived porous carbon/nickel/sulfur composite material and battery anode material prepared from same - Google Patents
Walnut shell derived porous carbon/nickel/sulfur composite material and battery anode material prepared from same Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 244
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 147
- 235000009496 Juglans regia Nutrition 0.000 title claims abstract description 144
- 235000020234 walnut Nutrition 0.000 title claims abstract description 144
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 116
- 239000002131 composite material Substances 0.000 title claims abstract description 109
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 101
- 239000011593 sulfur Substances 0.000 title claims abstract description 101
- 239000010405 anode material Substances 0.000 title claims abstract description 12
- 240000007049 Juglans regia Species 0.000 title 1
- 241000758789 Juglans Species 0.000 claims abstract description 143
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000013099 nickel-based metal-organic framework Substances 0.000 claims abstract description 8
- 238000004729 solvothermal method Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000012065 filter cake Substances 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 239000011268 mixed slurry Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000012257 stirred material Substances 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 abstract description 19
- 239000005077 polysulfide Substances 0.000 abstract description 19
- 150000008117 polysulfides Polymers 0.000 abstract description 19
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000012298 atmosphere Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 16
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003917 TEM image Methods 0.000 description 9
- 239000013543 active substance Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000006479 redox reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910018091 Li 2 S Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 238000013211 curve analysis Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
Abstract
The invention provides a walnut shell derived porous carbon/nickel/sulfur composite material and a battery anode material prepared from the same, wherein the preparation method of the walnut shell derived porous carbon/nickel/sulfur composite material comprises the following steps: 1) preparing walnut shell derived porous carbon WSAC; 2) preparing a walnut shell derived porous carbon/nickel composite material: mixing Ni (NO) 3 ) 2 ·6H 2 Placing the O into a conical bottle with a plug, adding N, N-dimethylformamide, dissolving and adding WSAC; mixing benzimidazole and N, N-dimethylformamide, adding into a conical flask with a plug, sealing, and stirring at 60 ℃; performing suction filtration, performing solvothermal reaction on the filter cake, washing with water and drying to obtain Ni-MOF/WSAC; under argonCarbonizing in the air atmosphere to obtain a walnut shell derived porous carbon/nickel composite material Ni-PC/WSAC; 3) preparing a walnut shell derived porous carbon/nickel/sulfur composite material; the invention has the beneficial effects of effectively carrying out physical confinement, chemical adsorption and catalytic conversion on polysulfide, and is suitable for the field of composite battery anode materials.
Description
Technical Field
The invention relates to the technical field of composite battery anode materials, in particular to a walnut shell derived porous carbon/nickel/sulfur composite material and a battery anode material prepared from the same.
Background
The traditional lithium-sulfur battery takes sulfur as a battery anode and metal lithium as a battery cathode, the theoretical specific capacity of the material and the theoretical specific energy of the battery are higher, and can respectively reach 1675mAh/g and 2600Wh/kg, which are far higher than the capacity of a widely applied lithium cobaltate battery, and the capacity of a lithium cobaltate battery is less than 150 mAh/g; and the sulfur has low price, rich storage capacity and environmental protection. However, lithium sulfur batteries are prone to poor conductivity, volume expansion, high preparation cost, shuttling effect of polysulfide intermediate, and other problems during use.
In recent years, in order to solve the above problems and improve the cycle performance of the battery, a great deal of research has been conducted on the modification of the composite positive electrode material, and a carbon material with high conductivity and a certain physical adsorption is selected as a sulfur carrier material, so that the waste biomass material greatly reduces the preparation cost, and the great attention has been paid. Among various biomass materials, such as coffee grounds, bamboo, cherry shells and the like, the biomass material has the defects of low porosity, low specific surface area, difficult material taking and the like. In addition, the physical adsorption of the non-polar carbon material to polysulfide cannot effectively limit the shuttle effect, and on the basis, a polar catalyst is introduced, such as doped heteroatom, supported metal and metal compound, etc., and chemical adsorption and catalytic conversion are performed on the carbon material through bonding with polysulfide, so that although the non-polar characteristic of the carbon material is improved and the shuttle effect of the polysulfide is effectively limited, the catalyst supported on the surface of the carbon material is easy to agglomerate, and when the size of the catalyst is larger, the provided active sites are less, the chemical adsorption effect is very limited, the pore size is small, and the physical confinement effect of the porous carbon material with low porosity on the polysulfide is not obvious.
In summary, in the process of preparing the sulfur cathode composite material, the preparation cost is high, or the catalyst is loaded on the surface of the carbon material, or the catalyst is loaded in the large carbon pores, so that the function is single, and the dual functions of physical confinement and chemical adsorption cannot be achieved at the same time.
Disclosure of Invention
Aiming at the defects in the related technology, the technical problem to be solved by the invention is as follows: the walnut shell derived porous carbon/nickel/sulfur composite material can effectively carry out physical confinement, chemical adsorption and catalytic conversion on polysulfide.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a walnut shell derived porous carbon/nickel/sulfur composite material comprises the following steps:
1) preparing walnut shell derived porous carbon WSAC;
2) preparing a walnut shell derived porous carbon/nickel composite material:
0.6 to 4.8g of Ni (NO) 3 ) 2 ·6H 2 Placing O into a conical bottle with a plug, adding 40mL of N, N-dimethylformamide, dissolving, and adding 0.3g of WSAC prepared in the step 1);
then respectively mixing 0.52-4.16 g of benzimidazole and 20ml of N, N-dimethylformamide, adding the mixture into a conical flask with a plug, sealing, and stirring for 24 hours at the temperature of 60 ℃;
performing suction filtration on the stirred material, then placing a filter cake in an autoclave reaction kettle with a polytetrafluoroethylene lining, performing solvothermal reaction for 6-24 h in a forced air drying oven at 170 ℃, and performing water washing and drying after the reaction is finished to obtain Ni-MOF/WSAC;
then heating to 700-900 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, and carbonizing for 0.5-3 h to obtain the walnut shell derived porous carbon/nickel composite material Ni-PC/WSAC;
3) preparing a walnut shell derived porous carbon/nickel/sulfur composite material:
mixing and grinding Ni-PC/WSAC and elemental sulfur uniformly according to the mass ratio of 3:7, placing the mixture in a high-pressure reaction kettle, keeping the temperature at 155 ℃ for 12 hours, and then heating to 180 ℃ for 1 hour to obtain the walnut shell derived porous carbon/nickel/sulfur composite material S @ Ni-PC/WSAC.
Preferably, the method for preparing walnut shell-derived porous carbon in step 1) comprises the steps of:
repeatedly and alternately ultrasonically cleaning walnut shells in ultrapure water and ethanol for three times; after drying treatment, carbonizing for 3h in the atmosphere of argon at 500 ℃, and then ball-milling for 6h in a ball mill to obtain carbide powder; then uniformly mixing carbide powder with a particle size of less than 100 meshes with KOH according to a mass ratio of 1:6, heating and stirring the mixture on a magnetic stirrer to slurry state, and activating the mixture for 2 hours at 800 ℃ under the argon atmosphere;
adding 2mol/L hydrochloric acid after activation, stirring for 12h, then standing and sucking out the supernatant; repeatedly adding hydrochloric acid, stirring until the supernatant is clear, and washing with ultrapure water to neutrality;
and (5) drying in a drying oven at 95 ℃ for 12h to obtain the walnut shell derived porous carbon WSAC.
Preferably, the particle size of the nano-grade nickel particles in the walnut shell derived porous carbon/nickel/sulfur composite material is 4.5-41.6 nm.
Preferably, the walnut shells are waste walnut shells.
The invention also provides a battery anode material prepared from the walnut shell derived porous carbon/nickel/sulfur composite material, which comprises the following raw materials: 50-150 mg of mixed slurry and 1-2 ml of N-methyl-2-pyrrolidone; wherein the mass ratio of the mixed slurry is as follows: walnut shell-derived porous carbon/nickel/sulfur composite material: acetylene black: polyvinylidene fluoride is 7:2: 1;
the walnut shell derived porous carbon/nickel/sulfur composite material is the walnut shell derived porous carbon/nickel/sulfur composite material.
Preferably, the preparation method of the battery cathode material comprises the following steps:
uniformly mixing the walnut shell derived porous carbon/nickel/sulfur composite material, acetylene black and polyvinylidene fluoride; then adding N-methyl-2-pyrrolidone, stirring to form slurry, and then blade-coating on an aluminum foil; drying in a drying oven at 60 ℃ for 12h, and finally cutting into circular pole pieces with the diameter of 12mm by using a slicing machine, namely the battery positive electrode material.
Preferably, the loading amount of sulfur on the circular pole piece is 1.0mg/cm 2 。
The invention has the beneficial technical effects that:
1. the walnut shell derived porous carbon/nickel/sulfur composite material prepared by the method has high content of active sulfur, the sulfur content is about 70%, the actual energy density of the lithium-sulfur battery can be improved, and the electrochemical performance of the lithium-sulfur battery can be improved. The prepared walnut shell derived porous carbon/nickel/sulfur composite material effectively realizes multiple functions of physical space limitation, chemical adsorption and catalytic conversion on polysulfide.
The invention adopts walnut shell derived porous carbon WSAC as a carbon substrate, which has 3000m 2 g -1 The carbon substrate has good conductivity and certain adsorbability, and the microporous structure can limit physical space. In the step 2), the nickel-based metal framework Ni-MOF is loaded into pores of the WSAC and then carbonized into nano-scale nickel particles, the nickel particles are uniformly distributed in micropores of a carbon substrate, rich active sites are provided, polysulfide can be limited in a microporous structure with high porosity, shuttle diffusion of polysulfide is effectively inhibited, and polysulfide is catalytically promoted to a reaction product Li 2 S 2 /Li 2 The conversion of S is adapted to the volume expansion of the active substance in the discharging process, so that the utilization rate of the active substance is greatly improved, and the cycle service life of the battery can be prolonged; meanwhile, the loading of the nickel particles can improve the non-polar characteristic of the carbon substrate, and the adsorbability to polysulfide is further enhanced; in addition, the WSAC pore channels can accelerate the diffusion and transfer of lithium ions and promote the redox reaction process of the lithium-sulfur battery.
The particle size of the nano-grade nickel particles prepared by the method is 4.5-41.6 nm, and Ni (NO) in the preparation process of the walnut shell derived porous carbon/nickel composite material is adjusted 3 ) 2 ·6H 2 The addition amount of O and benzimidazole, the solvothermal reaction time, the carbonization time and the temperature can be controlled, the particle size can be controlled, the nickel particles with smaller particle size have higher metal utilization rate and lower weight density, and the nickel particles are uniformly distributed on the carbon substrate, so that more active sites can promote the redox reaction of active substance sulfur, thereby promotingThe electrochemical performance of the battery.
2. According to the invention, walnut shells are treated as a biomass material to obtain walnut shell derived porous carbon, the walnut shells are carbonized in the preparation process, carbide powder is obtained by ball milling, and KOH is added to carry out an activation reaction on the carbide powder, so that the spatial microporous structure of the carbide powder is more unobstructed, and the prepared walnut shell derived porous carbon is used as a carbon substrate to better load nickel particles.
The residue of KOH was removed by adding hydrochloric acid.
3. The method adopts cheap and easily-obtained porous carbon derived from the waste walnut shells as the carbon substrate, meets the preparation requirement of the porous carbon/nickel/sulfur composite material derived from the walnut shells, simultaneously utilizes the waste walnut shells, is convenient to obtain materials, and reduces the cost.
4. The sulfur loading capacity of the battery anode material prepared from the walnut shell derived porous carbon/nickel/sulfur composite material is about 1.0mg/cm 2 The method can improve the actual energy density of the lithium-sulfur battery and improve the electrochemical performance of the lithium-sulfur battery.
Drawings
FIG. 1 is an SEM image at 10 μm of walnut shell-derived porous carbon WSAC prepared in accordance with the present invention;
FIG. 2 is an SEM image of part A at 0.5 μm of walnut shell derived porous carbon WSAC prepared in accordance with the present invention;
fig. 3 is an electron microscope image of a walnut shell-derived porous carbon/nickel composite material provided in example five of the present invention; wherein a1 is an SEM picture at 0.5 μm, a2 is a TEM picture at 200nm, a3 is a TEM picture at 50nm, a4 is a TEM picture at 5 nm;
fig. 4 is an electron microscope image of a walnut shell-derived porous carbon/nickel composite material provided in the sixth embodiment of the present invention; wherein b1 is an SEM image at 0.5 μm, b2 is a TEM image at 200nm, b3 is a TEM image at 50nm, b4 is a TEM image at 5 nm;
fig. 5 is an electron microscope image of a walnut shell-derived porous carbon/nickel composite material provided by the seventh embodiment of the present invention; wherein c1 is an SEM picture at 0.5 μm, c2 is a TEM picture at 200nm, c3 is a TEM picture at 50nm, c4 is a TEM picture at 5 nm;
FIG. 6 is a thermogravimetric plot of a walnut shell derived porous carbon/nickel composite material provided by the present invention;
FIG. 7 is a thermogravimetric plot of a walnut shell-derived porous carbon/nickel/sulfur composite provided by the present invention and a walnut shell-derived porous carbon/sulfur composite provided by a comparative example;
FIG. 8 is a cycle curve at 0.5C for a walnut shell-derived porous carbon/nickel/sulfur composite provided by the present invention and a walnut shell-derived porous carbon/sulfur composite provided by a comparative example;
FIG. 9 is a cycle curve at 1C for a walnut shell derived porous carbon/nickel/sulfur composite provided by the present invention;
FIG. 10 is a graph of the rate of change of a walnut shell derived porous carbon/nickel/sulfur composite provided by the present invention and a walnut shell derived porous carbon/sulfur composite provided by a comparative example;
in the figure: 10 is a thermogravimetric curve of the walnut shell-derived porous carbon/nickel composite material prepared in example five, 20 is a thermogravimetric curve of the walnut shell-derived porous carbon/nickel composite material prepared in example six, and 30 is a thermogravimetric curve of the walnut shell-derived porous carbon/nickel composite material prepared in example seven;
11 is a thermogravimetric curve of the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in the fifth example, 21 is a thermogravimetric curve of the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in the sixth example, 31 is a thermogravimetric curve of the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in the seventh example, and 41 is a thermogravimetric curve of the walnut shell-derived porous carbon/sulfur composite material provided in the comparative example;
12 is the cycle curve at 0.5C for the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in example five, 22 is the cycle curve at 0.5C for the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in example six, 32 is the cycle curve at 0.5C for the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in example seven, and 42 is the cycle curve at 0.5C for the walnut shell-derived porous carbon/sulfur composite material provided in comparative example;
13 is a cycle curve of the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in example five at 1C, 23 is a cycle curve of the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in example six at 1C, and 33 is a cycle curve of the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in example seven at 1C;
14 is the rate curve of the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in example five, 24 is the rate curve of the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in example six, 34 is the rate curve of the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in example seven, and 44 is the rate curve of the walnut shell-derived porous carbon/sulfur composite material provided in the comparative example.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples one to seven Ni (NO) as specified in table 1 below 3 ) 2 ·6H 2 O, benzimidazole, solvent thermal reaction time 1, temperature 1 and carbonization time 2, wherein the walnut shell derived porous carbon/nickel/sulfur composite material is prepared by the preparation method, and the preparation method comprises the following steps:
1) preparation of walnut shell-derived porous carbon WSAC:
repeatedly and alternately ultrasonically cleaning walnut shells in ultrapure water and ethanol for three times; after drying treatment, carbonizing for 3h in the atmosphere of argon at 500 ℃, and then ball-milling for 6h in a ball mill to obtain carbide powder; then uniformly mixing carbide powder with a particle size of less than 100 meshes with KOH according to the mass ratio of 1:6, heating and stirring the mixture on a magnetic stirrer to be slurry, and then activating the slurry for 2 hours at the temperature of 800 ℃ under the argon atmosphere;
adding 2mol/L hydrochloric acid after activation, stirring for 12h, then standing and sucking out the supernatant; repeatedly adding hydrochloric acid, stirring until the supernatant is clear, and washing with ultrapure water to neutrality;
drying in a drying oven at 95 ℃ for 12h to obtain the walnut shell derived porous carbon WSAC;
2) preparing a walnut shell derived porous carbon/nickel composite material:
ni (NO) of 3 ) 2 ·6H 2 Placing O into a conical bottle with a plug, adding 40mL of N, N-dimethylformamide, dissolving, and adding 0.3g of WSAC prepared in the step 1);
then mixing the benzimidazole and 20ml of N, N-dimethylformamide respectively, adding the mixture into a conical flask with a plug, sealing, and stirring for 24 hours at the temperature of 60 ℃;
performing suction filtration on the stirred material, then placing a filter cake in a high-pressure kettle reaction kettle with a polytetrafluoroethylene lining, performing solvothermal reaction in an air-blast drying oven at 170 ℃ for 1, and performing water washing and drying after the reaction is finished to obtain Ni-MOF/WSAC;
then heating to 1 ℃ at a heating rate of 5 ℃/min in an argon atmosphere for carbonization for 2 to obtain the walnut shell derived porous carbon/nickel composite material Ni-PC/WSAC;
3) preparing a walnut shell derived porous carbon/nickel/sulfur composite material:
mixing and grinding Ni-PC/WSAC and elemental sulfur uniformly according to the mass ratio of 3:7, placing the mixture in a high-pressure reaction kettle, keeping the temperature at 155 ℃ for 12 hours, and then heating to 180 ℃ for 1 hour to obtain the walnut shell derived porous carbon/nickel/sulfur composite material S @ Ni-PC/WSAC.
The walnut shell derived porous carbon/nickel/sulfur composite material prepared by the method has high content of active sulfur, the sulfur content is about 70%, the actual energy density of the lithium-sulfur battery can be improved, and the electrochemical performance of the lithium-sulfur battery can be improved. The prepared walnut shell derived porous carbon/nickel/sulfur composite material effectively realizes multiple functions of physical space limitation, chemical adsorption and catalytic conversion on polysulfide.
The invention adopts walnut shell derived porous carbon WSAC as a carbon substrate, which has 3000m 2 g -1 The large specific surface area, high porosity and natural microporous structure on the left and right, which has good conductivity and a carbon substrateThe adsorption property is fixed, and the micropore structure can play a role in limiting physical space. In the step 2), the nickel-based metal framework Ni-MOF is loaded into pores of the WSAC and then carbonized into nano-scale nickel particles, the nickel particles are uniformly distributed in micropores of a carbon substrate, rich active sites are provided, polysulfide can be limited in a microporous structure with high porosity, shuttle diffusion of polysulfide is effectively inhibited, and polysulfide is catalytically promoted to a reaction product Li 2 S 2 /Li 2 The conversion of S is adapted to the volume expansion of the active substance in the discharging process, so that the utilization rate of the active substance is greatly improved, and the cycle service life of the battery can be prolonged; meanwhile, the loading of nickel particles can improve the non-polar characteristic of the carbon substrate, and the adsorbability to polysulfide is further enhanced; in addition, the WSAC has the pore channels capable of accelerating the diffusion and transfer of lithium ions and promoting the oxidation-reduction reaction process of the lithium-sulfur battery.
According to the invention, walnut shells are treated as a biomass material to obtain walnut shell derived porous carbon, the walnut shells are carbonized in the preparation process, carbide powder is obtained by ball milling, and KOH is added to carry out an activation reaction on the carbide powder, so that the spatial microporous structure of the carbide powder is more unobstructed, and the prepared walnut shell derived porous carbon is used as a carbon substrate to better load nickel particles. The residue of KOH was removed by the addition of hydrochloric acid.
In particular, the Ni (NO) 3 ) 2 ·6H 2 The weight ratio of O to benzimidazole was 1.15: 1.
Further, the walnut shells are waste walnut shells.
The method adopts cheap and easily-obtained porous carbon derived from the waste walnut shells as the carbon substrate, meets the preparation requirement of the porous carbon/nickel/sulfur composite material derived from the walnut shells, simultaneously utilizes the waste walnut shells, is convenient to obtain materials, and reduces the cost.
TABLE 1
As can be seen from Table 1, the particle size of the nano-nickel particles in the walnut shell derived porous carbon/nickel/sulfur composite material is 4.5-41.6 nm.
The particle size of the nano-grade nickel particles prepared by the method is 4.5-41.6 nm, and Ni (NO) in the preparation process of the walnut shell derived porous carbon/nickel composite material is adjusted 3 ) 2 ·6H 2 The addition amount of O and benzimidazole, the solvothermal reaction time, the carbonization time and the temperature can be controlled, the particle size can be controlled, the nickel particles with smaller particle size have higher metal utilization rate and lower weight density, and the nickel particles are uniformly distributed on the carbon substrate, so that more active sites can promote the redox reaction of active substance sulfur, and the electrochemical performance of the battery is promoted.
Comparative example
A preparation method of a walnut shell derived porous carbon/sulfur composite material comprises the following steps:
1) preparing walnut shell derived porous carbon;
2) preparing a walnut shell derived porous carbon/sulfur composite material:
uniformly mixing and grinding the walnut shell derived porous carbon and elemental sulfur according to the mass ratio of 3:7, placing the mixture in a high-pressure reaction kettle, keeping the mixture at the temperature of 155 ℃ for 12 hours, and then heating the mixture to 180 ℃ for 1 hour to obtain the walnut shell derived porous carbon/sulfur composite material S @ WSAC.
In order to better understand the essence of the invention, parameters of specific surface area and pore diameter of the prepared WSAC and the walnut shell derived porous carbon/nickel composite material Ni-PC/WSAC prepared in the fifth to seventh examples are detected, and the detection results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the walnut shell derived porous carbon/nickel composite material Ni-PC/WSAC has a large specific surface area and a large pore size, can provide rich active sites for active sulfur, can limit polysulfide in a microporous structure with high porosity, and effectively inhibits shuttle diffusion of polysulfideAnd catalytically promoting polysulfides to the reaction product Li 2 S 2 /Li 2 The conversion of S is adapted to the volume expansion of the active substance in the discharging process, the utilization rate of the active substance is greatly improved, the cycle service life of the battery can be prolonged, and the cycle service life of the battery can be prolonged.
Fig. 1 is an SEM image at 10 μm of walnut shell-derived porous carbon WSAC prepared in accordance with the present invention, and fig. 2 is an SEM image at 0.5 μm of a portion in walnut shell-derived porous carbon WSAC prepared in accordance with the present invention; as can be seen from fig. 1 and 2, the walnut shell-derived porous carbon WSAC prepared by the invention has a unobstructed spatial microporous structure as a carbon substrate, and can better load nickel particles.
FIG. 3 is an electron micrograph of a walnut shell derived porous carbon/nickel composite material provided in example five of the present invention, wherein a1 is an SEM image at 0.5 μm, a2 is a TEM image at 200nm, a3 is a TEM image at 50nm, and a4 is a TEM image at 5 nm; FIG. 4 is an electron micrograph of a walnut shell derived porous carbon/nickel composite material provided in example six of the present invention, wherein b1 is an SEM image at 0.5 μm, b2 is a TEM image at 200nm, b3 is a TEM image at 50nm, and b4 is a TEM image at 5 nm; fig. 5 is an electron micrograph of a walnut shell-derived porous carbon/nickel composite material provided in example seven of the present invention, wherein c1 is an SEM at 0.5 μm, c2 is a TEM at 200nm, c3 is a TEM at 50nm, and c4 is a TEM at 5 nm.
As can be seen from fig. 3, 4 and 5, the nano nickel particles can be uniformly dispersed in the carbon substrate material, and no significant agglomeration occurs. In the fifth embodiment, the sixth embodiment and the seventh embodiment, the size of the nickel nanoparticle is controlled by controlling the solvothermal reaction time of the Ni-MOF/WSAC, namely the growth time of the Ni-MOF. The particle size of the nano-nickel particles prepared by the method is 4.5-41.6 nm, the nickel particles with smaller particle size have higher metal utilization rate and lower weight density, and more active sites of the nickel particles uniformly distributed on the carbon substrate can promote the redox reaction of active substance sulfur, so that the electrochemical performance of the battery is promoted.
FIG. 6 is a thermogravimetric plot of a walnut shell derived porous carbon/nickel composite material provided by the present invention; FIG. 7 is a thermogravimetric plot of a walnut shell-derived porous carbon/nickel/sulfur composite provided by the present invention and a walnut shell-derived porous carbon/sulfur composite provided by a comparative example; as can be seen from fig. 6 and 7, the content of nickel in the walnut shell-derived porous carbon/nickel/sulfur composite material prepared by the method is about 10 wt%, the sulfur loading is about 70%, and compared with the comparative example, the sulfur loading is increased by about 10%, and the increased sulfur loading can improve the actual energy density of the lithium-sulfur battery and the electrochemical performance of the lithium-sulfur battery.
FIG. 8 is a cycle curve at 0.5C for a walnut shell-derived porous carbon/nickel/sulfur composite provided by the present invention and a walnut shell-derived porous carbon/sulfur composite provided by a comparative example; FIG. 9 is a cycle curve at 1C for a walnut shell derived porous carbon/nickel/sulfur composite provided by the present invention; FIG. 10 is a graph of the rate of change of a walnut shell derived porous carbon/nickel/sulfur composite provided by the present invention and a walnut shell derived porous carbon/sulfur composite provided by a comparative example;
as can be seen from fig. 8, 9 and 10, as the particle size of the nano nickel particles is reduced, the capacity and rate performance of the battery are significantly improved. When the particle diameter of the nano nickel particles is 4.5nm, the first-circle capacity is 1205.0mAh g under the discharge rate of 0.2C -1 Capacity 961.0mAh g after 100 cycles -1 Above, the capacity fade rate was 0.202%. Under the discharge rate of 0.5C, the first-circle capacity is 1086.5mAh g -1 Capacity 834.6mAh g after 200 cycles -1 Above, the capacity fade rate was 0.116%. First-turn capacity 1101.55mAh g under 1C discharge rate -1 Capacity 851.77mAh g after 300 cycles -1 Above, the capacity fade rate was 0.075%. The capacities are 980.1 and 591.35mAh g at 2C and 3C multiplying power respectively -1 。
The invention also provides a battery anode material prepared from the walnut shell derived porous carbon/nickel/sulfur composite material, which comprises the following raw materials: mixing 50-150 mg of slurry and 1-2 ml of N-methyl-2-pyrrolidone; wherein the mass ratio of the mixed slurry is as follows: walnut shell-derived porous carbon/nickel/sulfur composite material: acetylene black: polyvinylidene fluoride is 7:2: 1; the walnut shell derived porous carbon/nickel/sulfur composite material is the walnut shell derived porous carbon/nickel/sulfur composite material.
Further, the preparation method of the battery cathode material comprises the following steps: uniformly mixing the walnut shell derived porous carbon/nickel/sulfur composite material, acetylene black and polyvinylidene fluoride; then adding N-methyl-2-pyrrolidone, stirring to form slurry, and then blade-coating on an aluminum foil; drying in a drying oven at 60 ℃ for 12h, and finally cutting into circular pole pieces with the diameter of 12mm by using a slicer, namely the battery anode material.
Further, the loading amount of sulfur on the circular pole piece is 1.0mg/cm 2 。
The sulfur loading capacity of the battery anode material prepared from the walnut shell derived porous carbon/nickel/sulfur composite material is about 1.0mg/cm 2 The method can improve the actual energy density of the lithium-sulfur battery and improve the electrochemical performance of the lithium-sulfur battery.
It should be noted that, in order to save space and achieve the purpose of conciseness and conciseness, electron microscopic image analysis, thermogravimetric analysis and cycle curve analysis are performed on the walnut shell-derived porous carbon/nickel composite material and the walnut shell-derived porous carbon/nickel/sulfur composite material prepared in the fifth to seventh embodiments.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
It will be appreciated that the relevant features of the above methods may be referred to one another. In addition, "first", "second", and the like in the above embodiments are for distinguishing the embodiments, and do not represent merits of the embodiments.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. A walnut shell derived porous carbon/nickel/sulfur composite material is characterized in that: the preparation method comprises the following steps:
1) preparing walnut shell derived porous carbon WSAC;
2) preparing a walnut shell derived porous carbon/nickel composite material:
0.6 to 4.8g of Ni (NO) 3 ) 2 ·6H 2 Placing O into a conical bottle with a plug, adding 40mL of N, N-dimethylformamide, dissolving, and adding 0.3g of WSAC prepared in the step 1);
then respectively mixing 0.52-4.16 g of benzimidazole and 20ml of N, N-dimethylformamide, adding the mixture into a conical flask with a plug, sealing, and stirring for 24 hours at the temperature of 60 ℃;
performing suction filtration on the stirred material, then placing a filter cake in an autoclave reaction kettle with a polytetrafluoroethylene lining, performing solvothermal reaction for 6-24 h in a forced air drying oven at 170 ℃, and performing water washing and drying after the reaction is finished to obtain Ni-MOF/WSAC;
then heating to 700-900 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, and carbonizing for 0.5-3 h to obtain the walnut shell derived porous carbon/nickel composite material Ni-PC/WSAC;
3) preparing a walnut shell derived porous carbon/nickel/sulfur composite material:
mixing and grinding Ni-PC/WSAC and elemental sulfur uniformly according to the mass ratio of 3:7, placing the mixture in a high-pressure reaction kettle, keeping the temperature at 155 ℃ for 12 hours, and then heating to 180 ℃ for 1 hour to obtain the walnut shell derived porous carbon/nickel/sulfur composite material S @ Ni-PC/WSAC.
2. The walnut shell-derived porous carbon/nickel/sulfur composite material of claim 1, wherein: the method for preparing walnut shell derived porous carbon in step 1) comprises the following steps:
repeatedly and alternately ultrasonically cleaning walnut shells in ultrapure water and ethanol for three times; carbonizing for 3h in an argon atmosphere at 500 ℃ after drying treatment, and then ball-milling for 6h in a ball mill to obtain carbide powder; uniformly mixing carbide powder with a particle size of less than 100 meshes with KOH according to a mass ratio of 1:6, heating and stirring the mixture on a magnetic stirrer to slurry, and activating the slurry for 2 hours at 800 ℃ under the argon atmosphere;
adding 2mol/L hydrochloric acid after activation, stirring for 12h, then standing and sucking out the supernatant; repeatedly adding hydrochloric acid, stirring until the supernatant is clear, and washing with ultrapure water to neutrality;
and (5) drying in a drying oven at 95 ℃ for 12h to obtain the walnut shell derived porous carbon WSAC.
3. The walnut shell-derived porous carbon/nickel/sulfur composite material of claim 1, wherein:
the particle size of the nano-grade nickel particles in the walnut shell derived porous carbon/nickel/sulfur composite material is 4.5-41.6 nm.
4. The walnut shell-derived porous carbon/nickel/sulfur composite material of claim 1, wherein:
the walnut shell is waste walnut shell.
5. A battery anode material prepared from walnut shell derived porous carbon/nickel/sulfur composite material is characterized in that: the method comprises the following raw materials: mixing 50-150 mg of slurry and 1-2 ml of N-methyl-2-pyrrolidone; wherein the mass ratio of the mixed slurry is as follows: walnut shell-derived porous carbon/nickel/sulfur composite material: acetylene black: polyvinylidene fluoride is 7:2: 1;
the walnut shell-derived porous carbon/nickel/sulfur composite material is the walnut shell-derived porous carbon/nickel/sulfur composite material as claimed in any one of claims 1 to 4.
6. The battery positive electrode material prepared from the walnut shell-derived porous carbon/nickel/sulfur composite material as claimed in claim 5, wherein: the preparation method of the battery positive electrode material comprises the following steps:
uniformly mixing the walnut shell derived porous carbon/nickel/sulfur composite material, acetylene black and polyvinylidene fluoride; then adding N-methyl-2-pyrrolidone, stirring to form slurry, and then blade-coating on an aluminum foil; drying in a drying oven at 60 ℃ for 12h, and finally cutting into circular pole pieces with the diameter of 12mm by using a slicing machine, namely the battery positive electrode material.
7. The battery positive electrode material prepared from the walnut shell-derived porous carbon/nickel/sulfur composite material as claimed in claim 6, wherein: the loading amount of sulfur on the circular pole piece is 1.0mg/cm 2 。
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