CN116826005B - Black phosphorus composite material for negative electrode of sodium ion battery and preparation method and application thereof - Google Patents
Black phosphorus composite material for negative electrode of sodium ion battery and preparation method and application thereof Download PDFInfo
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- CN116826005B CN116826005B CN202310901013.5A CN202310901013A CN116826005B CN 116826005 B CN116826005 B CN 116826005B CN 202310901013 A CN202310901013 A CN 202310901013A CN 116826005 B CN116826005 B CN 116826005B
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- ball milling
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- ion battery
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 37
- 239000006258 conductive agent Substances 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims description 94
- 239000011324 bead Substances 0.000 claims description 80
- 239000006230 acetylene black Substances 0.000 claims description 58
- 239000000843 powder Substances 0.000 claims description 49
- 239000000463 material Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- 238000007873 sieving Methods 0.000 claims description 13
- 238000000713 high-energy ball milling Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000010303 mechanochemical reaction Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 abstract description 14
- 150000002500 ions Chemical class 0.000 abstract description 12
- 229910052708 sodium Inorganic materials 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 2
- 239000006181 electrochemical material Substances 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000010935 stainless steel Substances 0.000 description 85
- 229910001220 stainless steel Inorganic materials 0.000 description 85
- 238000000227 grinding Methods 0.000 description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 30
- 230000002441 reversible effect Effects 0.000 description 16
- 229910052786 argon Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000010405 anode material Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 238000011056 performance test Methods 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005580 one pot reaction Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002272 high-resolution X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- -1 quantum dots Chemical compound 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a black phosphorus composite material for a negative electrode of a sodium ion battery, and a preparation method and application thereof, and belongs to the technical field of preparation and application of electrochemical materials. The black phosphorus composite material is prepared from black phosphorus, na-beta (beta') -Al 2 O 3 And a conductive agent carbon, said black phosphorus, na- β (β ") -Al 2 O 3 And the mass ratio of the conductive agent carbon is 6-8:1-3:1-2. The invention uses black phosphorus and Na-beta (beta) -Al 2 O 3 And conducting agent carbon to prepare a composite material, thereby realizing the integrated construction of an ion/electron conducting network in the battery cathode material. In the composite material prepared by the invention, black phosphorus can be combined with carbon and Na-beta (beta) -Al 2 O 3 And the compact contact is formed, so that the ionic and electronic conductivity of the black phosphorus composite material can be effectively improved, and meanwhile, P-C, al-P and P-O-C bonds can be formed to improve the structural stability of the black phosphorus sodium storage.
Description
Technical Field
The invention relates to the technical field of preparation and application of electrochemical materials, in particular to a black phosphorus composite material for a negative electrode of a sodium ion battery, and a preparation method and application thereof.
Background
Lithium ion batteries are widely used secondary battery technology at present, but lithium has the problems of uneven resource distribution, low reserve and the like, so that the cost of the lithium ion batteries is increased, and the requirement of large-scale application is difficult to meet. Sodium ion batteries have comparable performance to lithium ion batteries, particularly with a high reserve and low cost, are considered to be a beneficial supplement or replacement for lithium ion batteries, and exhibit large-scale energy storageExcellent application prospect. In recent years, researchers at home and abroad focus on research and development of high-performance sodium ion battery anode materials, such as: carbon materials, metal compounds, metal/nonmetal elements, etc. Among the materials for the negative electrode, black phosphorus has been attracting great research interest, since black phosphorus is the most stable phosphorus allotrope at normal temperature and pressure, it has a layered structure similar to graphite, and its theoretical specific capacity is high, and it has a good electron conductivity (10 2 S/m)。
However, there are two key problems with the practical application of black phosphorus cathodes: (1) The electron/ion conductivity of phosphorus is poor, so that the kinetics of oxidation-reduction reaction is slow during sodium storage, and the rate capability is poor; (2) The phosphorus negative electrode is an alloy sodium storage mechanism material, and has a huge sodium storage volume effect, so that the circulation stability is poor. In the report disclosed at present, black phosphorus is compounded with a carbon material or black phosphorus, carbon and titanium dioxide are compounded, and on one hand, the method can improve the electronic conductivity; on the other hand, P-C bond or Ti-O-P bond can be constructed to relieve volume effect to a certain extent, and improve sodium storage stability; however, the problems of ionic conductivity of the material are ignored in the method, so that the effect of improving the rate performance is poor. It is well known that electrochemical reactions require the co-participation of ions and electrons, which also adversely affects the kinetics of the sodium storage reaction if only the electron conductivity is improved and the ion conductivity is ignored. Therefore, developing a simple, effective and easily-expanded method for constructing an ion/electron integrated conductive network, and inhibiting the volume effect of the black phosphorus while improving the black phosphorus multiplying power performance is a technical problem to be solved.
Disclosure of Invention
First, the technical problem to be solved
In view of the above-mentioned shortcomings and disadvantages of the prior art, the invention provides a black phosphorus composite material for a sodium ion battery negative electrode, and a preparation method and application thereof, which solve the technical problems of poor rate capability and poor cycle stability of the black phosphorus negative electrode material.
(II) technical scheme
In order to achieve the above purpose, the main technical scheme adopted by the invention comprises the following steps:
in a first aspect, embodiments of the present invention provide a black phosphorus composite for a negative electrode of a sodium ion battery, the black phosphorus composite comprising black phosphorus, na- β (β ") -Al 2 O 3 And a conductive agent carbon, and reacting black phosphorus with the conductive agent carbon and Na-beta (beta') -Al by mechanochemical reaction 2 O 3 Forming dense contact with each other to form phosphorus-carbon bond (P-C), aluminum-phosphorus bond (Al-P) and phosphorus-oxygen-carbon bond (P-O-C), and the black phosphorus, na-beta (beta') -Al 2 O 3 And the mass ratio of the conductive agent carbon is 6-8:1-3:1-2.
Optionally, the black phosphorus and the Na- β (β ") -Al 2 O 3 Is of a size of micrometer or less.
Optionally, the conductive agent carbon has a size of nanometer or less.
Optionally, the conductive agent carbon is acetylene black.
In a second aspect, an embodiment of the present invention provides a method for preparing the black phosphorus composite material, where black phosphorus, na- β (β ") -Al are under the protection of inert gas 2 O 3 And ball milling with conductive agent carbon to obtain the final product.
Optionally, the ball milling adopts a high-energy planetary ball mill for ball milling; the rotation speed of the ball milling is 600-800rpm/min, and the ball milling time is 2-12h; the ball milling mode is unidirectional rotation ball milling.
Alternatively, ball milling adopts ball milling beads with different grades, and the ball milling beads are mixed with black phosphorus and Na-beta (beta) -Al 2 O 3 The ball-to-material ratio between the mixture of the conductive agent and the conductive agent is 20-50:1.
optionally, the black phosphorus is block black phosphorus, and the black phosphorus is obtained by ball milling and sieving under the protection of inert gas, wherein the size of the black phosphorus is below micron; or directly sieving the powder black phosphorus to obtain black phosphorus with the size below micron.
Optionally, the ball milling adopts a high-energy planetary ball mill for ball milling; the rotation speed of the ball milling is 600-800rpm/min, and the ball milling time is 1-6h; ball milling adopts ball milling beads with different grades, and the ball material ratio of the ball milling beads to the bulk black phosphorus is 20-50:1, ball milling is carried out in a unidirectional rotary type; the sieve pore diameter used for sieving is 800-1600 meshes.
Optionally, the ball-milling beads are stainless steel balls, and the inert gas is argon.
In a third aspect, an embodiment of the present invention provides a sodium ion battery, where a negative electrode of the sodium ion battery uses the black phosphorus composite material or the black phosphorus composite material prepared by the preparation method.
(III) beneficial effects
The beneficial effects of the invention are as follows: the invention relates to a black phosphorus composite material for a sodium ion battery cathode, a preparation method and application thereof, and black phosphorus, conductive carbon and sodium fast ion conductor Na-beta (beta) -Al 2 O 3 The composite material is obtained through high-energy ball milling and compounding, and the integrated construction of an ion/electron conductive network inside the composite material is realized. After high-energy ball milling, black phosphorus can be mixed with conductive agent carbon and Na-beta (beta) -Al 2 O 3 The compact contact is formed, the ionic conductivity and the electronic conductivity can be effectively improved, meanwhile, the P-C, al-P and P-O-C bonds can be formed, the structural stability of the black phosphorus sodium storage in the composite material is improved, and further, excellent multiplying power and circulation stability are obtained.
The black phosphorus-Na-beta (beta) -Al prepared by the invention 2 O 3 The carbon composite anode material overcomes the defect and the defect that the ion conductivity of the composite anode material is difficult to be effectively improved only by using the conductive carbon, the conductive carbon and titanium dioxide composition or the conductive polymer and other prior art schemes in the prior art. In the prior art, the conductive carbon and the conductive polymer are used for improving the electronic conductivity, and titanium dioxide is added to construct Ti-O-P bonds, so that the structural stability can be improved, but similar titanium dioxide, titanium nitride, sodium titanate, aluminum oxide and the like are not sodium fast ion conductors, and the improvement effect on the multiplying power performance of a sodium ion battery is poor. The invention constructs an ion/electron integrated conductive network, and among a plurality of fast ion conductors, na-beta (beta) -Al 2 O 3 Widely used as high Wen Naliu battery electrolyte, which has stable room temperature, low cost, easy preparation and high Na + Conductivity, etc. The invention adopts black phosphorus, na-beta (beta) -Al 2 O 3 And conductive agent carbon three materialsThe composite anode material, the compact ion/electron conductive network structure is formed after the three materials are compounded and ball-milled, and the three materials have a synergistic effect, so that the rate capability and the cycle stability of the sodium ion battery can be obviously improved.
In the preparation method provided by the invention, black phosphorus and Na-beta (beta) -Al 2 O 3 All can be micron-sized powder, and the prior art has certain requirements on the quality or the size of black phosphorus or additives, such as quantum dots, nanometer-sized and the like, and requires more strict process. The invention uses micron-sized black phosphorus and Na-beta (beta') -Al 2 O 3 The negative electrode of the sodium ion battery can be prepared, and the electrochemical performance is good.
The black phosphorus-Na-beta (beta) -Al prepared by the invention 2 O 3 Carbon composite negative electrode material, which has excellent reversible capacity and cycle stability as a negative electrode of a sodium ion battery, and particularly has superior rate capability of 0.1Ag -1 And 1.0Ag -1 The actual specific capacity of (a) is nearly equal and is obviously superior to the prior art.
The invention uses ball milling beads with different particle sizes to mix black phosphorus powder, na-beta (beta) -Al 2 O 3 The powder and the conductive agent carbon powder are subjected to ball milling, so that the ball milling is more uniform, uneven grinding caused by gaps generated by single-particle-size ball milling can be avoided, and a compact conductive network structure can be formed more easily.
The preparation method has the advantages of low cost, short period, strong operability, large batch yield, stable product performance and high reproducibility.
Drawings
FIG. 1 is a schematic diagram of micron-sized black phosphorus powder (A), commercially available Na-. Beta. (. Beta.) -Al obtained by ball milling and sieving in example 1 2 O 3 (B) And a Scanning Electron Microscope (SEM) image of the commercial conductive agent acetylene black (C). The scales are all 1 μm.
FIG. 2 is a schematic diagram of the preparation of Black Phosphorus (BP) -Na-. Beta. (. Beta.) -Al in example 1 2 O 3 -Scanning Electron Microscope (SEM) pictures of acetylene black composite.
FIG. 3 is a schematic diagram of the preparation of Black Phosphorus (BP) -Na-. Beta. (. Beta.) -Al in example 1 2 O 3 Acetylene black composite materialX-ray diffraction (XRD) pattern of the material.
FIG. 4 is a schematic diagram of the preparation of Black Phosphorus (BP) -Na-. Beta. (. Beta.) -Al in example 1 2 O 3 P2P (a), al 2P (B), C1 s (C) high resolution X-ray photoelectron spectroscopy (XPS) map of acetylene black composite.
FIG. 5 is a schematic diagram of the preparation of Black Phosphorus (BP) -Na-. Beta. (. Beta.) -Al in example 1 2 O 3 Acetylene black composite material used as negative electrode of sodium ion battery in 1Ag -1 Charge-discharge curve at current density.
FIG. 6 is a schematic diagram of the preparation of Black Phosphorus (BP) -Na-. Beta. (. Beta.) -Al in example 1 2 O 3 Acetylene black composite material used as negative electrode of sodium ion battery in 0.1Ag -1 Charge-discharge curve at current density.
FIG. 7 is a schematic diagram of the preparation of Black Phosphorus (BP) -Na-beta (beta') -Al in example 1 2 O 3 -graph of the rate cycle performance (a) and the cycle stability performance (B) of acetylene black composite used as negative electrode of sodium ion battery.
FIG. 8 is a schematic diagram of the preparation of Black Phosphorus (BP) -Na-. Beta. (. Beta.) -Al in example 2 2 O 3 Acetylene black composite material used as negative electrode of sodium ion battery in 1Ag -1 Charge-discharge curve at current density.
FIG. 9 is a one pot yield of 3g of Black Phosphorus (BP) -Na-. Beta. (. Beta.) -Al obtained in example 3 2 O 3 Acetylene black composite material used as negative electrode of sodium ion battery in 1Ag -1 Charge-discharge curve at current density.
FIG. 10 is a one pot yield of 5g of Black Phosphorus (BP) -Na-beta (beta') -Al obtained in example 4 2 O 3 Acetylene black composite material used as negative electrode of sodium ion battery in 1Ag -1 Charge-discharge curve at current density.
FIG. 11 is a one pot yield of 10g of Black Phosphorus (BP) -Na-beta (beta') -Al obtained in example 5 2 O 3 Acetylene black composite material used as negative electrode of sodium ion battery in 1Ag -1 Charge-discharge curve at current density.
FIG. 12 is a graph of 1Ag for preparing Black Phosphorus (BP) -acetylene black composite material used as negative electrode of sodium ion battery in comparative example 1 -1 A charge-discharge curve (a) and a cycle stability (B) at current density.
FIG. 13 is a diagram showing the preparation of Black Phosphorus (BP) -Na-. Beta. (. Beta.) -Al in comparative example 2 2 O 3 Composite material used as negative electrode of sodium ion battery in 1Ag -1 A charge-discharge curve (a) and a cycle stability (B) at current density.
FIG. 14 shows the preparation of Red Phosphorus (RP) -Na-. Beta. (. Beta.) -Al in comparative example 3 2 O 3 Acetylene black composite material used as negative electrode of sodium ion battery in 1Ag -1 Charge-discharge curve at current density.
FIG. 15 is a dry stirring and mixing process for preparing Black Phosphorus (BP) -Na-beta (beta) -Al in comparative example 4 using a stirrer 2 O 3 Acetylene black composite material used as negative electrode of sodium ion battery in 1Ag -1 Charge-discharge curve at current density.
Detailed Description
The present invention is not limited to the following specific embodiments, and equivalent changes based on the technical scheme of the present application fall within the protection scope of the present invention. The experimental methods in the following examples are conventional methods unless otherwise specified. The test materials used in the examples below are all commercially available, and unless otherwise specified, all default reagents are purchased as they are.
Example 1
This example provides a Black Phosphorus (BP) -Na-beta (beta') -Al 2 O 3 The preparation method of the acetylene black composite anode material comprises the following steps:
(1) In a dry glove box ([ O) filled with argon 2 ],[H 2 O]Less than or equal to 0.01 ppm), placing 2g of block black phosphorus and stainless steel ball grinding beads into a 50mL stainless steel ball grinding tank, wherein the total mass of the stainless steel ball grinding beads is 60g, and the stainless steel ball grinding beads comprise 3 stainless steel ball grinding beads with the diameter of 10mm, 6 stainless steel ball grinding beads with the diameter of 7mm and 20 stainless steel ball grinding beads with the diameter of 3mm, namely, the ball-to-material ratio is 30:1 (mass ratio), setting the ball milling rotating speed as 600rpm, setting the specific operation mode as one-way operation ball milling, wherein the ball milling time is 6 hours, sieving the obtained powder through a 800-mesh sieve after the ball milling is finished, and obtaining the Black Phosphorus (BP) powder with the micron-sized (0.2-2 mu m).
(2)In a dry glove box ([ O) filled with argon 2 ],[H 2 O]In less than or equal to 0.01 ppm), 0.9g of micron-sized (0.2-2 mu m) black phosphorus powder obtained in the step (1) and commercial micron-sized (0.5-3 mu m) Na-beta (beta') -Al 2 O 3 0.45g of powder and 0.15g of commercial nano-scale (50-100 nm) acetylene black C powder are placed in a 50mL stainless steel ball mill tank, and the total mass of the stainless steel ball mill beads is 45g, wherein the stainless steel ball mill beads comprise 3 stainless steel ball mill beads with the diameter of 10mm, 6 stainless steel ball mill beads with the diameter of 7mm and 15 stainless steel ball mill beads with the diameter of 3mm, namely the ball material ratio is 30:1 (mass ratio) to carry out unidirectional rotation ball milling, wherein the ball milling rotating speed is set to 600rpm, the ball milling time is 6 hours, and BP-Na-beta (beta) -Al is obtained after the operation is finished 2 O 3 -acetylene black composite.
As shown in FIG. 1, micron-sized black phosphorus powder (A) obtained by ball milling and sieving and commercially available Na-beta (beta) -Al are shown 2 O 3 (B) And SEM pictures of the commercial conductive agent acetylene black (C) (all scales 1 μm), black phosphorus and Na-beta (beta ") -Al are seen 2 O 3 The size is micron or submicron, and the acetylene black is nano-sized particles.
As shown in fig. 2, which is an SEM image of the composite material, it can be seen that it is difficult to efficiently distinguish Na- β (β ") -Al after ball milling 2 O 3 And an acetylene black phase, indicating black phosphorus, na-beta (beta') -Al 2 O 3 And acetylene black achieve uniform mixing and dense contact.
As shown in FIG. 3, the XRD pattern of the composite material shows that the black phosphorus phase is hardly changed after ball milling by comparing with the XRD pattern of a single phase, and Na-beta (beta) -Al can be clearly observed at a diffraction angle 2 theta of about 8 degrees 2 O 3 Characteristic diffraction peaks.
As shown in FIG. 4, the P2P, al 2P and C1 s high-resolution XPS patterns of the composite material prove that the P-C bond, the P-O-C bond and the P-Al bond exist in the composite sample. From the above, the composite anode material prepared by the invention does not simply adopt Black Phosphorus (BP) and Na-beta (beta) -Al 2 O 3 Mixing acetylene black, and mechanically and chemically reacting (ball milling) black phosphorus with carbon as conductive agent and Na-beta (beta) -Al 2 O 3 Form dense contact with each other to form phosphorus-The existence of carbon bond (P-C), aluminum-phosphorus bond (Al-P) and phosphorus-oxygen-carbon bond (P-O-C) greatly improves the structural stability of the composite material, builds an ion/electron integrated conductive network in the composite material, improves the black phosphorus multiplying power performance and simultaneously suppresses the volume effect.
Electrochemical performance test:
the composite material prepared by the method is used for the negative electrode of a sodium ion battery, and BP-Na-beta (beta) -Al is adopted 2 O 3 Acetylene black composite material, acetylene black (conductive agent), sodium carboxymethyl cellulose and styrene-butadiene rubber (binder) in mass ratio of 85:5:3:7, uniformly mixing and coating the mixture on an aluminum foil in a proportion, wherein the coating thickness is 20-100 mu m, and preparing the electrode plate after vacuum drying and cutting. The battery assembling and performance testing method comprises the following steps:
in a dry glove box ([ O) filled with argon 2 ],[H 2 O]Less than or equal to 0.01 ppm) for assembling the CR2025 button cell. Transferring the prepared dry electrode slice into a glove box, matching with metal sodium slice (counter electrode and reference electrode), separating with glass fiber membrane, and dripping several points of 1M NaPF 6 Electrolyte solution containing 5wt% of FEC additive dissolved in DMC EC EMC (volume ratio 1:1:1); finally, the cell was sealed and left to stand for 6 hours. The static battery is placed in a new Wei battery test system for testing, wherein: the charge-discharge cut-off voltage window is set to 0.01V-2.5V; the charge and discharge are carried out by adopting a constant current mode, and the current density is set to be 1.0Ag -1 And 0.1Ag -1 . The experimental results are shown in FIGS. 5-6.
As shown in FIG. 5, at 1.0Ag -1 A charge-discharge curve at current density, a specific capacity of about 1200mAhg for initial discharge -1 The subsequent reversible capacity is about 1080mAhg -1 . As shown in FIG. 6, at 0.1Ag -1 A charge-discharge curve at current density, a specific capacity of about 1300mAhg for initial discharge -1 The subsequent reversible capacity is approximately 1210mAhg -1 。
The composite material was further tested for rate cycle performance and cycle stability as a negative electrode of a sodium ion battery, and the test results are shown in fig. 7. From the graph, the composite anode material has excellent rate performance (0.2 Ag -1 And 1.0Ag -1 Reversible capacities of 1020mAhg respectively -1 And 980mAhg -1 ) And cycle stability (reversible capacities of 1200mAhg for 1 st, 2 nd and 50 th turns, respectively -1 、1070mAhg -1 And 995mAhg -1 ) The application prospect is good.
Example 2
This example provides a method for preparing BP-Na-beta (beta) -Al using commercially available powder black phosphorus 2 O 3 -a method of acetylene black composite anode material comprising the steps of:
in a dry glove box ([ O) filled with argon 2 ],[H 2 O]Less than or equal to 0.01 ppm), 0.9g of black phosphorus of the micron-sized (2-5 μm) powder sold in the market and Na-beta (beta') -Al of the micron-sized (0.5-3 μm) powder sold in the market are added 2 O 3 0.45g of powder and 0.15g of commercial nano-scale (50-100 nm) acetylene black C powder are placed in a 50mL stainless steel ball mill tank, and the total mass of the stainless steel ball mill beads is 45g, wherein the stainless steel ball mill beads comprise 3 stainless steel ball mill beads with the diameter of 10mm, 6 stainless steel ball mill beads with the diameter of 7mm and 15 stainless steel ball mill beads with the diameter of 3mm, namely the ball material ratio is 30:1 (mass ratio) to carry out unidirectional rotation ball milling, wherein the ball milling rotating speed is set to 800rpm, the ball milling time is 12 hours, and BP-Na-beta (beta) -Al is obtained after the operation is finished 2 O 3 -acetylene black composite.
Electrochemical performance test:
the composite material prepared by the method is used for the negative electrode of a sodium ion battery, and BP-Na-beta (beta) -Al is adopted 2 O 3 Acetylene black composite material, acetylene black (conductive agent), sodium carboxymethyl cellulose and styrene-butadiene rubber (binder) in mass ratio of 85:5:3:7, uniformly mixing and coating the mixture on an aluminum foil with the coating thickness of 20-100 mu m, and preparing the electrode plate after vacuum drying and cutting. Battery assembly and performance test method referring to example 1, the test results are shown in fig. 8: at 1Ag -1 A charge-discharge curve at current density having a specific capacity of approximately 1180mAhg for initial discharge -1 The subsequent reversible capacity is about 960mAhg -1 And has cycle stability similar to that of example 1, while having excellent rate performance (0.2 Ag -1 And 1.0Ag -1 Reversible capacity is 980mAhg respectively -1 And 920mAhg -1 )。
Example 3
This example provides a one pot preparation of 3g Black Phosphorus (BP) -Na-beta (beta') -Al 2 O 3 -a method of acetylene black composite anode material comprising the steps of:
(1) In a dry glove box ([ O) filled with argon 2 ],[H 2 O]Less than or equal to 0.01 ppm), placing 5g of block black phosphorus and stainless steel ball grinding beads into a 50mL stainless steel ball grinding tank, wherein the total mass of the stainless steel ball grinding beads is 100g, and the stainless steel ball grinding beads comprise 10 stainless steel ball grinding beads with the diameter of 10mm, 20 stainless steel ball grinding beads with the diameter of 7mm and 50 stainless steel ball grinding beads with the diameter of 3mm, namely, the ball-to-material ratio is 20:1 (mass ratio), setting the ball milling rotating speed to 800rpm, wherein the specific operation mode is one-way operation ball milling, the ball milling time is 1 hour, and sieving the obtained powder through a 800-mesh sieve after the ball milling is finished to obtain micron-sized Black Phosphorus (BP) powder (0.2-2 mu m).
(2) In a dry glove box ([ O) filled with argon 2 ],[H 2 O]2.4g of micron-sized (0.2-2 μm) black phosphorus powder obtained in the step (1) and commercial micron-sized (0.5-3 μm) Na-beta (beta') -Al are added in the amount of less than or equal to 0.01ppm 2 O 3 0.3g of powder and 0.3g of commercial nanometer (50-100 nm) acetylene black C powder are placed in a 50mL stainless steel ball mill tank, and the total mass of the stainless steel ball mill beads is 150g, and the stainless steel ball mill comprises 10 stainless steel ball mill beads with the diameter of 10mm, 20 stainless steel ball mill beads with the diameter of 7mm and 80 stainless steel ball mill beads with the diameter of 3mm, namely the ball-to-material ratio of 50:1 (mass ratio) to carry out unidirectional rotation ball milling, wherein the ball milling rotating speed is set to 800rpm, the ball milling time is 2 hours, and BP-Na-beta (beta) -Al is obtained after the operation is finished 2 O 3 -acetylene black composite.
Electrochemical performance test:
the composite material prepared by the method is used for the negative electrode of a sodium ion battery, and BP-Na-beta (beta) -Al is adopted 2 O 3 Acetylene black composite material, acetylene black (conductive agent), sodium carboxymethyl cellulose and styrene-butadiene rubber (binder) in a mass ratio of 80:10:3:7, uniformly mixing and coating the mixture on an aluminum foil in a proportion, wherein the coating thickness is 20-100 mu m, and preparing the electrode plate after vacuum drying and cutting. Method for assembling and testing the Performance of the Battery referring to example 1, testThe test results are shown in fig. 9: at 1Ag -1 A charge-discharge curve at a current density having a specific capacity of about 1310mAhg for initial discharge -1 The subsequent reversible capacity is approximately 1160mAhg -1 And has cycle stability similar to that of example 1, while having excellent rate performance (0.2 Ag -1 And 1.0Ag -1 Reversible capacity is 1025mAhg respectively -1 And 975mAhg -1 )。
Example 4
This example provides a one pot preparation of 5g Black Phosphorus (BP) -Na-beta (beta') -Al 2 O 3 -a method of acetylene black composite anode material comprising the steps of:
(1) In a dry glove box ([ O) filled with argon 2 ],[H 2 O]Less than or equal to 0.01 ppm), placing 5g of block black phosphorus and stainless steel ball grinding beads into a 50mL stainless steel ball grinding tank, wherein the total mass of the stainless steel ball grinding beads is 150g, and the stainless steel ball grinding beads comprise 10 stainless steel ball grinding beads with the diameter of 10mm, 20 stainless steel ball grinding beads with the diameter of 7mm and 80 stainless steel ball grinding beads with the diameter of 3mm, namely, the ball-to-material ratio is 30:1 (mass ratio), setting the ball milling rotating speed to 800rpm, wherein the specific operation mode is one-way operation ball milling, the ball milling time is 3 hours, and sieving the obtained powder through a 800-mesh sieve after the ball milling is finished to obtain micron-sized Black Phosphorus (BP) powder (0.2-2 mu m).
(2) In a dry glove box ([ O) filled with argon 2 ],[H 2 O]In less than or equal to 0.01 ppm), 3.5g of micron-sized (0.2-2 mu m) black phosphorus powder obtained in the step (1) and commercial micron-sized (0.5-3 mu m) Na-beta (beta') -Al are added 2 O 3 0.75g of powder and 0.75g of commercial nanometer-scale (50-100 nm) acetylene black C powder are placed in a 50mL stainless steel ball mill tank, and the total mass of the stainless steel ball mill beads is 200g, wherein the stainless steel ball mill beads comprise 12 stainless steel ball mill beads with the diameter of 10mm, 25 stainless steel ball mill beads with the diameter of 7mm and 100 stainless steel ball mill beads with the diameter of 3mm, namely the ball material ratio is 40:1 (mass ratio) to carry out unidirectional rotation ball milling, wherein the ball milling rotating speed is set to 800rpm, the ball milling time is 12 hours, and BP-Na-beta (beta) -Al is obtained after the operation is finished 2 O 3 -acetylene black composite.
Electrochemical performance test:
the manufacturing method of the electrode slice is seen inExample 3 battery assembly and performance test method referring to example 1, the test results are shown in fig. 10: FIG. 10 shows the preparation of BP-Na-beta (beta') -Al 2 O 3 Acetylene black composite material used as negative electrode of sodium ion battery and 1Ag -1 A charge-discharge curve at current density, a specific capacity of about 1290mAhg for initial discharge -1 The subsequent reversible capacity was approximately 1190mAhg -1 And has cycle stability similar to that of example 1, while having excellent rate performance (0.2 Ag -1 And 1.0Ag -1 Reversible capacities are 1040mAhg respectively -1 And 1000mAhg -1 )。
Example 5
This example provides a one pot preparation of 10g Black Phosphorus (BP) -Na-beta (beta') -Al 2 O 3 -a method of acetylene black composite anode material comprising the steps of:
(1) In a dry glove box ([ O) filled with argon 2 ],[H 2 O]Less than or equal to 0.01 ppm), 10g of block black phosphorus and stainless steel ball milling beads are placed in a 50mL stainless steel ball milling tank, the total mass of the stainless steel ball milling beads is 200g, and the stainless steel ball milling beads comprise 12 stainless steel ball milling beads with the diameter of 10mm, 25 stainless steel ball milling beads with the diameter of 7mm and 100 stainless steel ball milling beads with the diameter of 3mm, namely the ball material ratio is 20:1 (mass ratio), setting the ball milling rotating speed to 800rpm, setting the specific operation mode to unidirectional operation ball milling, wherein the ball milling time is 6 hours, sieving the obtained powder through a 1600-mesh sieve after ball milling is finished, and obtaining micron-sized Black Phosphorus (BP) powder (0.2-2 mu m).
(2) In a dry glove box ([ O) filled with argon 2 ],[H 2 O]7g of micron-sized (0.2-2 mu m) black phosphorus powder obtained in the step (1) and commercial micron-sized (0.5-3 mu m) Na-beta (beta') -Al are added in the amount of less than or equal to 0.01ppm 2 O 3 1.5g of powder and 1.5g of commercial nanometer (50-100 nm) acetylene black C powder are placed in a 50mL stainless steel ball mill tank, and the total mass of the stainless steel ball mill beads is 300g, wherein the stainless steel ball mill beads comprise 12 stainless steel ball mill beads with the diameter of 10mm, 25 stainless steel ball mill beads with the diameter of 7mm and 150 stainless steel ball mill beads with the diameter of 3mm, namely the ball material ratio is 30:1 (mass ratio) to carry out unidirectional rotation ball milling, wherein the ball milling rotating speed is set to 800rpm, the ball milling time is 6 hours, and BP-Na-beta (beta')-Al 2 O 3 -acetylene black composite.
Electrochemical performance test:
manufacturing method of electrode sheet referring to example 3, battery assembling and performance test method referring to example 1, and test results are shown in fig. 11: FIG. 11 shows the preparation of BP-Na-beta (beta') -Al 2 O 3 Acetylene black composite material used as negative electrode of sodium ion battery and 1Ag -1 A charge-discharge curve at current density having a specific capacity of about 1190mAhg for initial discharge -1 The subsequent reversible capacity is about 1170mAhg -1 And has cycle stability similar to that of example 1, while having excellent rate performance (0.2 Ag -1 And 1.0Ag -1 Reversible capacity is 1025mAhg respectively -1 And 975mAhg -1 )。
From the above examples, it can be concluded that: the invention provides Black Phosphorus (BP) -Na-beta (beta) -Al 2 O 3 The preparation method of the acetylene black composite material can effectively improve the ionic/electronic conductivity of the material, so that the material has high rate capability and cycle stability as a negative electrode of a sodium ion battery, and particularly the method is effective for both commercial block black phosphorus and powder black phosphorus, and has the advantages of low manufacturing cost, short period, strong operability, large batch yield, stable product performance and high reproducibility. The Black Phosphorus (BP) -Na-beta (beta) -Al prepared by the invention 2 O 3 The C composite material has better application prospect as a negative electrode of a sodium ion battery.
Comparative example 1
The comparative example provides a preparation method of a Black Phosphorus (BP) -acetylene black composite anode material, which comprises the following steps:
(1) In a dry glove box ([ O) filled with argon 2 ],[H 2 O]Less than or equal to 0.01 ppm), placing 2g of block black phosphorus and stainless steel ball grinding beads into a 50mL stainless steel ball grinding tank, wherein the total mass of the stainless steel ball grinding beads is 60g, and the stainless steel ball grinding beads comprise 3 stainless steel ball grinding beads with the diameter of 10mm, 6 stainless steel ball grinding beads with the diameter of 7mm and 20 stainless steel ball grinding beads with the diameter of 3mm, namely, the ball-to-material ratio is 30:1 (mass ratio), setting the ball milling rotating speed to 600rpm, the concrete operation mode is one-way operation ball milling, the ball milling time is 6 hours,after the ball milling, the obtained powder was sieved through a 800 mesh sieve to obtain micron-sized Black Phosphorus (BP) powder (0.2-2 μm).
(2) In a dry glove box ([ O) filled with argon 2 ],[H 2 O]0.9g of micron-sized (0.2-2 mu m) black phosphorus powder obtained in the step (1) and 0.6g of commercial nanometer-sized (50-100 nm) acetylene black C powder are placed in a 50mL stainless steel ball mill tank, and the total mass of the stainless steel ball mill beads is 45g, wherein the stainless steel ball mill beads comprise 3 stainless steel ball mill beads with the diameter of 10mm and 6 stainless steel ball mill beads with the diameter of 7mm and 15 stainless steel ball mill beads with the diameter of 3mm, namely the stainless steel ball mill beads with the ball material ratio of 30:1 (mass ratio) and the ball milling rotating speed is set to 600rpm, the ball milling time is 6 hours, and the BP-acetylene black composite material is obtained after the operation is finished.
Electrochemical performance test:
manufacturing method of electrode sheet referring to example 1, battery assembling and performance test method referring to example 1, and test results are shown in fig. 12: FIG. 12 shows that the Black Phosphorus (BP) -acetylene black composite material is prepared as a negative electrode of a sodium ion battery in 1Ag -1 A charge-discharge curve (A) and a cycle stability (B) at a current density, a specific capacity of about 760mAhg for initial discharge -1 And the reversible capacity of the 2 nd turn and the 50 th turn are 630mAhg respectively -1 And 520mAhg -1 。
Comparative example 2
This comparative example provides a Black Phosphorus (BP) -Na-beta (beta') -Al 2 O 3 The preparation method of the composite anode material comprises the following steps:
(1) In a dry glove box ([ O) filled with argon 2 ],[H 2 O]Less than or equal to 0.01 ppm), placing 2g of block black phosphorus and stainless steel ball grinding beads into a 50mL stainless steel ball grinding tank, wherein the total mass of the stainless steel ball grinding beads is 60g, and the stainless steel ball grinding beads comprise 3 stainless steel ball grinding beads with the diameter of 10mm, 6 stainless steel ball grinding beads with the diameter of 7mm and 20 stainless steel ball grinding beads with the diameter of 3mm, namely, the ball-to-material ratio is 30:1 (mass ratio), setting the ball milling rotating speed as 600rpm, setting the specific operation mode as one-way operation ball milling, wherein the ball milling time is 6 hours, sieving the obtained powder through a 800-mesh sieve after the ball milling is finished, and obtaining micron-sized Black Phosphorus (BP) powder (0.2-2 mu m).
(2) In a dry glove box ([ O) filled with argon 2 ],[H 2 O]In less than or equal to 0.01 ppm), 0.9g of micron-sized (0.2-2 mu m) black phosphorus powder obtained in the step (1) and commercial micron-sized (0.5-3 mu m) Na-beta (beta') -Al 2 O 3 0.6g of powder is placed in a 50mL stainless steel ball milling tank, the total mass of the stainless steel ball milling beads is 45g, and the powder comprises 3 stainless steel ball milling beads with the diameter of 10mm, 6 stainless steel ball milling beads with the diameter of 7mm and 15 stainless steel ball milling beads with the diameter of 3mm, namely, the powder is prepared by the following steps of: 1 (mass ratio) to carry out unidirectional rotation ball milling, wherein the ball milling rotating speed is set to 600rpm, the ball milling time is 6 hours, and BP-Na-beta (beta) -Al is obtained after the operation is finished 2 O 3 A composite material.
Electrochemical performance test:
manufacturing method of electrode sheet referring to example 1, battery assembling and performance testing method referring to example 1, and test results are shown in fig. 13: FIG. 13 shows the prepared Black Phosphorus (BP) -Na-beta (beta') -Al 2 O 3 Composite material used as negative electrode of sodium ion battery in 1Ag -1 A charge-discharge curve (A) and a cycle stability (B) at a current density, a specific capacity of about 840mAhg at the first discharge -1 And the reversible capacity of the 2 nd turn and the 50 th turn are 720mAhg respectively -1 And 600mAhg -1 。
It is demonstrated by comparative examples 1 and 2 that the same process was used, except that Na-. Beta. (. Beta.) -Al was not added 2 O 3 Or acetylene black does not achieve the excellent sodium storage performance in the embodiments of the present invention. The Black Phosphorus (BP), na-beta (beta') -Al in the present invention were demonstrated 2 O 3 And acetylene black is ball-milled to form a composite material with a synergistic effect, and compared with Black Phosphorus (BP) -Na-beta (beta) -Al 2 O 3 The composite material or the Black Phosphorus (BP) -acetylene black composite material can obviously improve the ionic/electronic conductivity of the material, thereby improving the multiplying power performance and the cycling stability of the sodium ion battery.
Comparative example 3
This comparative example is based on example 1, where the black phosphorus in example 1 was replaced with red phosphorus, the rest of the process being unchanged.
FIG. 14 shows the red phosphorus produced(RP)-Na-β(β″)-Al 2 O 3 Acetylene black composite material used as negative electrode of sodium ion battery in 1Ag -1 A charge-discharge curve at a current density having a specific capacity of about 830mAhg for initial discharge -1 The subsequent reversible capacity is only 710mAhg -1 。
The invention uses black phosphorus as a basic carrier, and the black phosphorus has ultrahigh theoretical specific capacity (about 2596mAhg -1 ) Preferred electron conductivity (102S/m) and suitable operating potential (0.35 Vvs. Na + Na) by mixing black phosphorus with Na-beta (beta') -Al 2 O 3 And the composite material is compounded with acetylene black and then ball-milled together to form a conductive network structure, so that the problem of poor electron/ion conductivity of black phosphorus is solved, the ion/electron diffusion characteristic is improved, and the electrochemical performance, particularly the rate performance and the cycling stability of the battery are remarkably improved after the composite material is prepared.
Comparative example 4
This comparative example was prepared by mixing micron-sized (0.2-2 μm) black phosphorus powder prepared in step (1) of example 1, commercially available micron-sized (0.5-3 μm) Na-. Beta. (. Beta.) -Al on the basis of example 1 2 O 3 Mixing the powder with commercial nano-scale (50-100 nm) acetylene black C powder by dry stirring by a stirrer, and mixing the obtained material with acetylene black (conductive agent), sodium carboxymethyl cellulose and styrene-butadiene rubber (adhesive) according to a mass ratio of 85:5:3:7, uniformly mixing and coating the mixture on an aluminum foil, and preparing the electrode plate after vacuum drying and cutting. The sodium ion battery assembly and performance test method were the same as in example 1.
FIG. 15 shows the preparation of Black Phosphorus (BP) -Na-beta (beta) -Al by dry stirring and mixing with a stirrer in this comparative example 2 O 3 Acetylene black composite material used as negative electrode of sodium ion battery in 1Ag -1 A charge-discharge curve at current density, a specific capacity of about 460mAhg for initial discharge -1 The capacity of the 2 nd turn is only 260mAhg -1 And the 3 rd turn capacity is almost negligible.
In example 1 of the present invention, since the black phosphorus powder of the micrometer scale, the na—β (β ") -Al of the micrometer scale 2 O 3 The powder and the nano-scale acetylene black C powder are compounded by high-energy ball milling to form a compact conductive network nodeThe structure of the invention successfully constructs an ion/electron integrated conductive network structure, thereby improving the multiplying power performance and the cycling stability of the sodium ion battery. This comparative example uses a direct mixing method, and cannot form a conductive network, so that the effect is far less than that of example 1.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. A black phosphorus composite material for a negative electrode of a sodium ion battery is characterized by comprising black phosphorus and Na-beta (beta) -Al 2 O 3 And conductive agent carbon, and mechanochemical reaction of black phosphorus with conductive agent carbon and Na- β (β') -Al by high energy ball milling 2 O 3 Forming compact contact with each other to form phosphorus-carbon bond, aluminum-phosphorus bond and phosphorus-oxygen-carbon bond; the black phosphorus, na-beta (beta') -Al 2 O 3 And the mass ratio of the conductive agent carbon is 6-8:1-3:1-2.
2. The black phosphorus composite for a negative electrode of a sodium ion battery according to claim 1, wherein the black phosphorus and Na- β (β ") -Al 2 O 3 Is of a size of micrometer or less.
3. The black phosphorus composite for a negative electrode of a sodium ion battery according to claim 1, wherein the conductive agent carbon has a size of nano-scale or less.
4. The black phosphorus composite for a negative electrode of a sodium ion battery according to claim 1, wherein the conductive agent carbon is acetylene black.
5. The black phosphorus composite of any of claims 1-4The preparation method of the material is characterized in that black phosphorus and Na-beta (beta) -Al are subjected to protection of inert gas 2 O 3 And carrying out high-energy ball milling on the conductive agent carbon to obtain the conductive agent.
6. The preparation method according to claim 5, wherein the rotation speed of the high-energy ball milling is 600-800rpm/min, and the time of the high-energy ball milling is 2-12h; the high-energy ball milling mode is unidirectional rotary ball milling.
7. The method according to claim 5 or 6, wherein the high-energy ball milling is performed by using ball milling beads with different grades, wherein the ball milling beads are mixed with black phosphorus and Na-beta (beta) -Al 2 O 3 And a conductive agent, wherein the ball-to-material ratio of the mixture of the three is 20-50:1.
8. the preparation method of claim 5, wherein the black phosphorus is block black phosphorus, and the black phosphorus is obtained by ball milling and sieving under the protection of inert gas, and has a size below micron; or directly sieving the powder black phosphorus to obtain black phosphorus with the size below micron.
9. The method according to claim 8, wherein the rotation speed of the ball mill is 600-800rpm/min, and the ball milling time is 1-6 hours; ball milling adopts ball milling beads with different grades, and the ball material ratio of the ball milling beads to the bulk black phosphorus is 20-50:1, ball milling is carried out in a unidirectional rotary type; the sieve pore diameter used for sieving is 800-1600 meshes.
10. A sodium ion battery, wherein a negative electrode of the sodium ion battery adopts the black phosphorus composite material according to any one of claims 1 to 4 or the black phosphorus composite material prepared by the preparation method according to any one of claims 5 to 9.
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| CN115360337A (en) * | 2022-09-14 | 2022-11-18 | 许昌学院 | Black phosphorus composite material with high-rate lithium storage performance and preparation method and application thereof |
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| CN116169260A (en) * | 2022-12-22 | 2023-05-26 | 三峡大学 | β”-Al 2 O 3 And N-doped C composite coated Na 3 V 2 (PO 4 ) 2 F 3 Electrode material |
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| CN113437281A (en) * | 2021-05-31 | 2021-09-24 | 天津市天大赛达协同创新科技研究院有限公司 | Black phosphorus-based negative electrode material and preparation method thereof |
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| CN115360337A (en) * | 2022-09-14 | 2022-11-18 | 许昌学院 | Black phosphorus composite material with high-rate lithium storage performance and preparation method and application thereof |
| CN115498165A (en) * | 2022-10-12 | 2022-12-20 | 哈尔滨工业大学 | Black phosphorus-based composite electrode and preparation method and application thereof |
| CN116169260A (en) * | 2022-12-22 | 2023-05-26 | 三峡大学 | β”-Al 2 O 3 And N-doped C composite coated Na 3 V 2 (PO 4 ) 2 F 3 Electrode material |
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