CN109824030A - A kind of hollow carbon sphere and its preparation method and application - Google Patents
A kind of hollow carbon sphere and its preparation method and application Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 241001502050 Acis Species 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 5
- 238000010931 ester hydrolysis Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 4
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 229940018563 3-aminophenol Drugs 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 3
- 238000005253 cladding Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 229960000935 dehydrated alcohol Drugs 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001453 impedance spectrum Methods 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LZOZLBFZGFLFBV-UHFFFAOYSA-N sulfene Chemical compound C=S(=O)=O LZOZLBFZGFLFBV-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Abstract
The invention discloses a kind of hollow carbon sphere and its preparation method and application, first preparation includes the solution of resin monomer, surfactant, ammonia, water, alcohol, then positive esters of silicon acis is added in solution, and silica suspension is prepared in positive silicic acid ester hydrolysis；Formalin is added in silica suspension, silica-resin compounded ball is prepared in polymerization reaction；By silica-resin compounded ball calcining, silica-carbon composite balls are prepared；By the silica in silica-carbon composite balls by acid or alkali removal, hollow carbon sphere is prepared.The present invention is by one-step synthesis silica-resin compounded ball, i.e., the problem of merging by the synthesis of silica and resin cladding process, solve prior art two-step method complex steps, need finely regulating.The hollow carbon sphere being prepared has controllable wall thickness, macropore appearance and bigger serface.
Description
Technical field
The invention belongs to carbon ball technical fields, and in particular to a kind of hollow carbon sphere and its preparation method and application.
Background technique
In the prior art, in the method and step using hard template method synthesis hollow carbon sphere are as follows: first, utilize ethyl orthosilicate
Hydrolysis prepares the good silica spheres of monodispersity；Second, the clean silica spheres of separating, washing are passed through into ultrasound
Method be evenly dispersed in solution, and silica is coated by the polymerization of presoma.Third, by the tree of acquisition
After the drying of rouge coated silica ball separating, washing, high temperature cabonization is carried out, to obtain carbon coating silica spheres.4th, benefit
Silica template is removed with acid or alkali, obtains hollow carbon sphere after separating, washing drying.Existing synthesis porous hollow carbon ball
There is some shortcomings during being synthetically prepared, for example, the preparation of silica template and Coated with Organic Matter globulation are point
What step carried out.For purified templates, it is also necessary to undergo additional washing, separation process.Coating Cheng Qian, it is also necessary to template
It is ultrasonically treated, keeps its evenly dispersed.During cladding, surfactant and reactant need a point multi-step to be added
Enter, complex steps, needs extremely subtly to regulate and control.In addition, the wall thickness of the hollow carbon sphere of prior art synthesis is bigger, and not
Uniformly.
Summary of the invention
The present invention in view of the above deficiencies, proposes that a kind of preparation method of hollow carbon sphere, the preparation method include following step
It is rapid:
(1) solution A comprising resin monomer, surfactant, ammonia, water and alcohol is first prepared, then institute is added in positive esters of silicon acis
It states in solution A, is denoted as solution B, silica suspension is prepared in positive silicic acid ester hydrolysis；
(2) formalin is added in the silica suspension of step (1), silica-is prepared in polymerization reaction
Resin compounded ball；
(3) silica of step (2)-resin compounded ball is calcined, silica-carbon composite balls is prepared；
(4) silica in the silica-carbon composite balls of step (3) is removed by acid or alkali, institute is prepared
State hollow carbon sphere.
Preparation method according to the present invention, in step (1) solution A, the resin monomer is selected from catechol, adjacent benzene two
At least one of amine, m-phenylene diamine (MPD), resorcinol, m-aminophenol and o-aminophenol；Resin monomer in the solution A
Molar concentration be 0.005mol/L~0.1mol/L, preferably in solution A the molar concentration of resin monomer be 0.01mol/L~
0.08mol/L, for example, molar concentration can be 0.025,0.05,0.075mol/L.
Preparation method according to the present invention, in step (1) solution A, the surfactant is selected from polyoxyethylene polyoxy third
Alkene ether block copolymers (such as F127, F123), triethylene tetramine, cetylamine, cetyl trimethylammonium bromide and cetyl
One of trimethyl ammonium chloride etc., two or more；The surfactant is preferably cetyl trimethylammonium bromide
And/or hexadecyltrimethylammonium chloride.The mass fraction of the surfactant be 0.01%~10%, preferably 0.02%~
1%, illustratively, mass fraction 0.02%.
Preparation method according to the present invention, in step (1) solution A, the alcohol is at least one in ethyl alcohol, propyl alcohol and butanol
Kind；The volume ratio of the alcohol and water is 1:7~4:1, such as 2:5,1:3,1:1,2:1.
Preparation method according to the present invention, the mass fraction of ammonia is 0.01%~0.5% in step (1) solution A, preferably
0.01%~0.05%, such as the mass fraction of ammonia is 0.01%.Solution A can be added in the ammonia in the form of ammonium hydroxide or ammonia
In.
Preparation method according to the present invention, in step (1) solution B, the positive esters of silicon acis is selected from methyl orthosilicate, positive silicic acid
At least one of ethyl ester and positive silicic acid propyl ester；Mass fraction of the positive esters of silicon acis in solution B is 1%~20%；Such as
3%, 5%, 7%, 10%, 15%.The temperature of the solution B is maintained at 15 DEG C~60 DEG C (preferably 40-60 DEG C), positive esters of silicon acis water
The time of solution is 1h~for 24 hours (preferably 1-2h), and positive silicic acid ester hydrolysis generates silica spheres during this, and the hydrolytic process is excellent
Choosing is with stirring.
Preparation method according to the present invention, in step (2), the molar ratio of the formaldehyde and the resin monomer be 1:1~
3:1；The formaldehyde is slowly added in silica suspension, and it is 0.1ml/ that preferably the rate of silica suspension, which is added, in formaldehyde
Min~10ml/min, such as 0.5ml/min, 1ml/min, 3ml/min, 5ml/min.It is added formaldehyde into the step (2)
After in silica suspension, first first stage polymerization reaction, the temperature of the first stage polymerization reaction is 35 DEG C~80 DEG C
(preferably 35 DEG C~50 DEG C), time are 8h~for 24 hours (preferably 20h~for 24 hours)；In order to react resin monomer sufficiently, described first
Second stage polymerization reaction is carried out after stage polymerization reaction again, second stage polymerization temperature is 80 DEG C~140 DEG C (preferably 80 DEG C
~90 DEG C), polymerization reaction time is 2h~30h (preferably 20h~30h), such as 5h, 10h, 15h, 20h, 25h, 30h；In order to anti-
Only solvent volatilizees in polymerization process, is preferably reacted in closed container, for example, by using hydro-thermal reaction.
Preparation method according to the present invention, in step (3), silica-resin compounded ball is calcined under an inert atmosphere, institute
Stating mainly has nitrogen, helium and/or argon gas in inert atmosphere, the calcination temperature be 400 DEG C~1000 DEG C, preferably 500 DEG C~
600 DEG C, such as 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C；The calcination time be 1h~20h, preferably 15h~20h, such as 3h,
6h, 9h, 12h, 15h, 18h, 20h.
Preparation method according to the present invention, in step (4), the acid can be hydrofluoric acid, and the alkali can be hydroxide
Sodium solution and/or potassium hydroxide solution；As an example, the alkali can be the KOH solution that concentration is 5~8mol/L.
Further, the present invention also provides hollow carbon sphere prepared by the preparation method, the hollow carbon sphere
Ball wall average thickness range is 5nm~100nm；The maximum particle diameter range of the hollow carbon sphere is 50nm~1000nm；Kong Rongwei
0.3~1.0m3g-1, specific surface area is 200~900m2g-1；Two, three or more in the more preferably described hollow carbon sphere
The ball wall of carbon ball is connected with each other.
Further, the present invention provides application of the hollow carbon sphere in supercapacitor.
Further, the present invention provides the application of the hollow carbon sphere in the battery；Preferably, the hollow carbon sphere application
In the electrode material of lithium-sulfur cell.
Further, the present invention provides the supercapacitor for containing the hollow carbon sphere.
Further, the present invention provides the lithium-sulfur cell for containing the hollow carbon sphere.
Beneficial effects of the present invention:
(1) present invention is by one-step synthesis silica-resin compounded ball, i.e., by the synthesis of silica and resin packet
The problem of process of covering merges, and solves prior art two-step method complex steps, needs finely regulating.
(2) the preparation-obtained hollow carbon sphere of preparation method of the present invention has controllable wall thickness, macropore appearance and bigger serface.
Detailed description of the invention
Fig. 1 is that the SEM for the hollow carbon sphere that embodiment 1 is prepared schemes (a) and TEM schemes (b).
Fig. 2 is that the SEM for the hollow carbon sphere that embodiment 2 is prepared schemes (a) and TEM schemes (b).
Fig. 3 is that the SEM for the hollow carbon sphere that embodiment 3 is prepared schemes (a) and TEM schemes (b).
Fig. 4 is the SEM figure for the hollow carbon sphere that comparative example 1 is prepared.
Fig. 5 is that the SEM for the solid carbon ball that comparative example 2 is prepared schemes (a) and TEM schemes (b).
Fig. 6 is the impedance spectrum of the supercapacitor in embodiment 21.
Fig. 7 is the impedance spectrum of the lithium-sulfur cell in embodiment 22.
Specific embodiment
Hollow carbon sphere and its preparation method and application of the invention is done further below in conjunction with specific embodiment
It is described in detail.It should be appreciated that the following example is merely illustrative the ground description and interpretation present invention, and it is not necessarily to be construed as to this hair
The limitation of bright protection scope.All technologies realized based on above content of the present invention are encompassed by the range the present invention is directed to protection
It is interior.
Unless otherwise indicated, raw materials and reagents used in the following embodiment are commercial goods, or can be by
Perception method preparation.
Following embodiment and comparative example instrument information:
Scanning electron microscope (SEM): Hitachi S-4800SEM.
Transmission electron microscope (TEM): Tecnai F30TEM.
Electrochemical workstation: CHI660E.
Embodiment 1
By resin monomer-resorcinol, ammonium hydroxide, deionized water, dehydrated alcohol, surfactant-cetyl trimethyl
Ammonium bromide (CTAB) is mixed evenly, and prepares solution A；Ethyl orthosilicate (TEOS) is added in solution A, solution B is prepared, is protected
The temperature for holding solution B is 40 DEG C, makes teos hydrolysis 1h, prepares silica suspension；With the rate of addition of 1ml/min
Into silica suspension liquid plus formalin, the progress first stage polymerization reaction at 35 DEG C are reacted for 24 hours；Again by solution
It is transferred in reaction kettle, keeping solution temperature is 80 DEG C, and carry out second stage polymerization: hydro-thermal reaction 30h prepares silica-
Resin compounded ball；After silica-resin compounded ball washing, filtering, drying, it is transferred in tube furnace, in the atmosphere of nitrogen
Under be warming up to 600 DEG C, keep the temperature 20h, prepare silica-carbon composite balls；By silica-carbon composite balls with hydrofluoric acid removal two
Silica, centrifugation, washing, drying, prepares hollow carbon sphere.Wherein the molar ratio of formaldehyde and the resin monomer is 2:1 in solution,
The additive amount of other substances is as shown in table 1.The carbon ball that embodiment 1 obtains is denoted as MF-5.5-20.
The SEM that Fig. 1 is the hollow carbon sphere MF-5.5-20 that embodiment 1 is prepared schemes (a) and TEM schemes (b), it will thus be seen that
The particle size of hollow carbon sphere is almost the same, about 250nm, and wall thickness is about 9nm, and between ball and ball be it is interconnected,
Explanation is further verified in this box marked in TEM figure.
Embodiment 2~10
Embodiment 2~10, preparation process is same as Example 1, only the molar concentration of resin monomer, the matter of positive esters of silicon acis
It is different to measure score, the mass fraction of surfactant, the volume ratio of alcohol and water, it is specific as shown in table 1.
The hollow carbon sphere that embodiment 2 obtains is denoted as MF-2.2-20, SEM schemes (a) and TEM figure (b) such as Fig. 2, can see
Out: the particle size of hollow carbon sphere is almost the same, about 250nm, and wall thickness is about 15nm, and is to be connected with each other between ball and ball
, explanation is further verified in this box marked in TEM figure.
The hollow carbon sphere that embodiment 3 obtains is denoted as MF-1.1-20, SEM schemes (a) and TEM figure (b) such as Fig. 3, can see
Out: the particle size of hollow carbon sphere is almost the same, about 250nm, and wall thickness is about 30nm, and is to be connected with each other between ball and ball
, explanation is further verified in this box marked in TEM figure.
Table 1.
Embodiment 11~20
Embodiment 11~20, preparation process is same as Example 1, only teos hydrolysis temperature and time, polymerization
Reaction temperature and time, calcination temperature and time difference, it is specific as shown in table 2.
Table 2.
Comparative example 1
The dehydrated alcohol of the deionized water for removing 50ml, 150ml are uniformly mixed and are to be saturated ammonium hydroxide adjusting solution ph
8.0,10ml ethyl orthosilicate (TEOS) is added in above-mentioned solution, solution temperature remains 60 DEG C, hydrolyzes 1h, prepares dioxy
SiClx suspension；Centrifugation, washing, drying prepare silicon oxide pellets.
Deionized water, ammonium hydroxide, dehydrated alcohol, cetyl trimethylammonium bromide are uniformly mixed in the ratio of embodiment 1,
Solution C is prepared, silicon oxide pellets are added in solution C, stirs evenly, prepares suspension D；The catechol of 3.3g is spent
It is added in suspension D after the dissolution of the mixed solution of ionized water and dehydrated alcohol, is added with the speed of 0.1ml/min into suspension D
The formalin for entering 6ml, solution is transferred in reaction kettle, and keeping solution temperature is 80 DEG C, and hydro-thermal reaction 30h prepares dioxy
SiClx-resin compounded ball；After silica-resin compounded ball washing, filtering, drying, it is transferred in tube furnace, in nitrogen
It is warming up to 400 DEG C under atmosphere, keeps the temperature 20h, prepares silica-carbon composite balls；Silica-carbon composite balls are gone with hydrofluoric acid
Except silica, centrifugation, washing, drying prepare hollow carbon sphere.
Fig. 4 is the SEM figure for the hollow carbon sphere that comparative example 1 is prepared, it will thus be seen that the porous hollow carbon ball being synthetically prepared
The particle size of middle ball is almost the same, about 200nm, is dispersion between ball and ball.
Comparative example 2
Deionized water, ammonium hydroxide, dehydrated alcohol, cetyl trimethylammonium bromide are uniformly mixed in the ratio of embodiment 1,
Solution E is prepared, will be added in solution E after the dissolution of the mixed solution of the catechol deionized water of 3.3g and dehydrated alcohol, with
The formalin of 6ml is added into solution E for the speed of 0.1ml/min, and solution is transferred in reaction kettle, and holding solution temperature is
80 DEG C, hydro-thermal reaction 30h, prepare resin balls；After resin balls washing, filtering, drying, it is transferred in tube furnace, in nitrogen
It is warming up to 400 DEG C under atmosphere, keeps the temperature 20h, prepares solid carbon ball.
Fig. 5 is that the SEM for the solid carbon ball that comparative example 2 is prepared schemes (a) and TEM schemes (b), it will thus be seen that is synthetically prepared
The good solid carbon ball of monodispersity, particle size are about 250nm out, be between ball and ball it is isolated, this can be in TEM figure
It obtains further verifying explanation.
The preparation of 21 supercapacitor of embodiment
The solid carbon ball of the resulting hollow carbon sphere of embodiment 1-3, comparative example 2, respectively with acetylene black and PTFE (polytetrafluoro
Ethylene) it is mixed by the mass ratio of 8:1:1, it then, is ground using dehydrated alcohol as solvent with ball mill, revolving speed 300r/
Min grinds 4h, obtains slurry.By resulting slurry coating on graphite paper, then, at 80 DEG C, 8h is dried with baking oven, is obtained
Electrode slice.Then by the electrode slice under 120 DEG C of vacuum conditions, dry 12h prepares the electrode slice of supercapacitor；By electrode
Piece, diaphragm, negative electrode tab successively stack, and add the KOH electrolyte of 6mol/l, are assembled into double electric layers supercapacitor.In 1A/g,
Three electrode constant current charge-discharge tests, test voltage window are carried out under the current density of 2A/g, 5A/g, 10A/g, 15A/g, 20A/g
For -1V-0V；Wherein, working electrode is the electrode slice of above-mentioned preparation, is platinum plate electrode to electrode, and reference electrode is calomel electrode,
Electrolyte is 6mol/L KOH solution.The results are shown in Table 3 for the specific capacitance measured.
Under open-circuit voltage values, testing impedance is carried out, test frequency range is 0.01HZ-100000HZ, and amplitude is
0.005V.Impedance spectrum is as shown in Figure 6.
The specific capacitance test result of 3. embodiment 1-3 of table and the supercapacitor of 2 carbon ball of comparative example preparation
As can be seen from Table 3: corresponding under identical current density with the reduction of porous hollow carbon ball wall thickness
Specific capacitance measured by electrode material for super capacitor is being continuously increased；In addition, being continuously increased with current density, can see
Porous hollow carbon ball wall is thinner out, and the specific capacitance storage rate under opposite 1A/g current density is higher, illustrates porous hollow carbon
Ball wall is thinner, and the high rate performance of the electrode material of corresponding supercapacitor is also better.
As can be seen from Figure 6: with the reduction of porous hollow sphere carbon ball wall thickness, semicircle is straight in high frequency region, impedance spectrum
Diameter is constantly reducing, i.e. the charge transfer resistance R of materialctConstantly reduce, in low frequency range, slope of a curve is continuously increased, i.e. material
Expect the capacitive character having had and small diffusion resistance, found from impedance test results, reduces porous hollow carbon ball wall thickness, favorably
In the high rate performance for improving supercapacitor.This result is consistent with the result of table 3.
The preparation of 22 lithium-sulfur cell of embodiment
The solid carbon ball of the resulting hollow carbon sphere of embodiment 1-3, comparative example 2, respectively and the ratio of elemental sulfur 3:7 in mass ratio
Example mixed grinding is uniform, then, will grind uniform carbon sulphur mixture and is added in carbon disulfide solvent, stirred at room temperature
It mixes, stirring rate 300r/min, after stirring 0.5h, resulting slurry is put into tube furnace, under the atmosphere of nitrogen, heating
Rate is 2 DEG C/min, is heated to 160 DEG C, keeps the temperature 12h, then furnace is as cold as room temperature.By above-mentioned resulting C/S mixture and carbon black
(super-P) and Kynoar (PVDF) is mixed in the ratio of 8:1:1, is molten with N-Methyl pyrrolidone (NMP)
Agent carries out ball milling, ball milling speed 300r/min, ball milling 4h.Then resulting slurry is uniformly coated on aluminium foil, is first existed
It is dried at a temperature of 80 DEG C, is then dried in vacuo the electrode slice of prebake under conditions of vacuum, 120 DEG C in advance
12h prepares electrode slice.Finally, for lithium as cathode, electrolyte is double trifluoros of 1mol/l using above-mentioned electrode slice as anode
Sulfonyl methane imine lithium (LiTFSI) is dissolved in 1,3-dioxolane (DOL)/glycol dimethyl ether (DME)=1:1 (volume ratio), and
Add the LiNO that mass percent is 1%3, lithium-sulfur cell is assembled into glove box.
At 30 DEG C, constant current charge-discharge survey is carried out under the current density of 0.2C, 0.5C, 1C, 2C, 3C, 5C and 10C respectively
Examination, test voltage window are 1.5-3.0V.The results are shown in Table 4 for the specific capacity that test obtains.
In addition, testing impedance is carried out under open-circuit voltage, test frequency 0.01HZ-100000HZ, amplitude 0.005V.
Impedance spectrum is as shown in Figure 7.
The specific capacity test result for the lithium-sulfur cell that the carbon ball of 4. embodiment 1-3 of table and comparative example 2 obtains
As can be seen from Table 4: under identical current density, as the wall thickness of hollow carbon sphere constantly reduces, corresponding electricity
The specific energy density of lithium-sulfur cell corresponding to the material of pole is continuously increased, and with the increase of current density, this phenomenon is especially bright
Aobvious, i.e., under high magnification, the specific energy density storage rate of lithium-sulfur cell corresponding to hollow carbon sphere is higher, i.e. times of lithium-sulfur cell
Rate performance is better.
As can be seen from Figure 7: with the continuous reduction of hollow carbon sphere wall thickness, the charge of lithium-sulfur cell corresponding to material is passed
Transmission of electricity resistance RctConstantly become smaller, that is, be conducive to the high rate performance for improving battery, this conclusion is consistent with the result of table 4.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of hollow carbon sphere, which is characterized in that the preparation method includes the following steps:
(1) solution A comprising resin monomer, surfactant, ammonia, water, alcohol is first prepared, then positive esters of silicon acis is added in solution A,
It is denoted as solution B, silica suspension is prepared in positive silicic acid ester hydrolysis；
(2) formalin is added in the silica suspension of step (1), silica-resin is prepared in polymerization reaction
Composite balls；
(3) silica of step (2)-resin compounded ball is calcined, silica-carbon composite balls is prepared；
(4) silica in the silica-carbon composite balls of step (3) is removed by acid or alkali, hollow carbon is prepared
Ball.
2. the preparation method of hollow carbon sphere according to claim 1, which is characterized in that in step (1) solution A, the resin
Monomer in catechol, o-phenylenediamine, m-phenylene diamine (MPD), resorcinol, m-aminophenol and o-aminophenol at least one
Kind；
The molar concentration of resin monomer is 0.005mol/L~0.1mol/L, resin monomer preferably in solution A in the solution A
Molar concentration is 0.01mol/L~0.03mol/L.
3. the preparation method of hollow carbon sphere according to claim 1, which is characterized in that in step (1) solution A, the surface
Activating agent is selected from polyoxyethylene poly-oxygen propylene aether block copolymer, triethylene tetramine, cetylamine, cetyl trimethylammonium bromide
With one of hexadecyltrimethylammonium chloride, two or more, preferred cetyl trimethylammonium bromide and/or 16
Alkyl trimethyl ammonium chloride；
The mass fraction of the surfactant is 0.01%~10%；
The mass fraction of ammonia is 0.01%~0.5%, preferably 0.01%~0.05% in the solution A.
4. the preparation method of hollow carbon sphere according to claim 1, which is characterized in that in step (1) solution A, the alcohol is
At least one of ethyl alcohol, propyl alcohol, butanol；
The volume ratio of the alcohol and water is 1:7~4:1.
5. the preparation method of hollow carbon sphere according to claim 1, which is characterized in that in step (1) solution B, the positive silicon
Acid esters is selected from least one of methyl orthosilicate, ethyl orthosilicate and positive silicic acid propyl ester；
Mass fraction of the positive esters of silicon acis in solution B is 1%~20%；
The temperature of the solution B is maintained at 15 DEG C~60 DEG C, and positive esters of silicon acis hydrolysis time is 1h~for 24 hours.
6. the preparation method of hollow carbon sphere according to claim 1, which is characterized in that in step (2), the formaldehyde is added two
The rate for aoxidizing silicon suspension is 0.1ml/min~10ml/min；
After being added formaldehyde into silica suspension in the step (2), first first stage polymerization reaction, first rank
The temperature of section polymerization reaction is 35 DEG C~80 DEG C, and the time is 8h~for 24 hours；Second is carried out after the first stage polymerization reaction again
Stage polymerization reaction, second stage polymerization temperature are 80 DEG C~140 DEG C, and polymerization reaction time is 2h~30h.
7. the preparation method of hollow carbon sphere according to claim 1, which is characterized in that in step (3), the calcination atmosphere is
Inert atmosphere mainly has nitrogen, helium and/or argon gas in the inert atmosphere；
The calcination temperature is 400 DEG C~900 DEG C, and calcination time is 1~20h.
8. the preparation method of hollow carbon sphere according to claim 1 or claim 2, which is characterized in that in the step (2), the first
The molar ratio of aldehyde and the resin monomer is 1:1~3:1.
9. a kind of hollow carbon sphere, which is characterized in that it is made by the method according to any one of claims 1 to 8, it is described hollow
Carbon ball includes that the ball wall of two, three or more carbon ball is connected with each other；
The ball wall average thickness of the hollow carbon sphere is 5nm~100nm；
The maximum particle diameter of the hollow carbon sphere is 100nm~800nm.
10. a kind of electrode of lithium-sulfur cell includes hollow carbon sphere as claimed in claim 9.
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