CN115196674B - Battery electrode composite material and preparation method and application thereof - Google Patents
Battery electrode composite material and preparation method and application thereof Download PDFInfo
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- CN115196674B CN115196674B CN202210788407.XA CN202210788407A CN115196674B CN 115196674 B CN115196674 B CN 115196674B CN 202210788407 A CN202210788407 A CN 202210788407A CN 115196674 B CN115196674 B CN 115196674B
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- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229940073609 bismuth oxychloride Drugs 0.000 claims abstract description 32
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- -1 transition metal oxychloride Chemical class 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 229910021381 transition metal chloride Inorganic materials 0.000 claims abstract description 5
- 150000003841 chloride salts Chemical class 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of composite materials, and discloses a battery electrode composite material, a preparation method and application thereof, wherein the preparation steps comprise the following steps of S1: dissolving cupric salt in organic solvent by ultrasonic wave, adding mixed solution of trimesic acid dissolved in organic solvent by ultrasonic wave, standing, adding organic solvent, centrifuging and drying to obtain CuBTC; s2: annealing CuBTC in an inert atmosphere to obtain a Cu@C precursor; s3: dissolving a Cu@C precursor and a transition metal chloride salt in an organic solvent, stirring, performing hydrothermal reaction, and centrifuging to obtain the flaky bismuth oxychloride. According to the battery electrode composite material and the preparation method, the flaky bismuth oxychloride has larger surface area, larger capacity and high sodium ion mobility, and meanwhile, the stability of the battery is improved through the synergistic effect of the flaky bismuth oxychloride and the transition metal oxychloride.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a battery electrode composite material, and a preparation method and application thereof.
Background
The current battery cathode material has lower capacity and can not meet the requirements of the current battery, wherein the capacity of the metal sulfide material is reduced due to volume expansion and shuttle effect in the charge and discharge process, and the cycle stability is poor. The transition metal oxychloride combines the transition metal and the oxygen element chlorine element, so that the capacity is higher, the shape of the material can be controlled, the volume expansion of the material in the charge and discharge process can be effectively inhibited, the shuttle effect can be relieved to a certain extent, and better circulation stability can be obtained.
The transition metal sulfide can provide high capacity due to electron transfer reaction in the charge and discharge process, but the stability and the rate capability of the transition metal sulfide are poor due to side reaction between sodium metal and electrolyte, so that the transition metal sulfide has an inefficient sodium storage process, and further the application of the transition metal sulfide in sodium ion batteries is limited.
Disclosure of Invention
Aiming at the technical problems of poor shuttle effect, poor cycle stability, poor multiplying power performance and the like of a metal sulfide material and a transition metal sulfide serving as an electrode material in the prior art, the invention provides a battery electrode composite material, a preparation method and application thereof, and particularly prepares a bismuth oxychloride (BiOCl) classical layered structure material consisting of [ Cl-Bi-O-Bi-Cl ] slices containing alloy type metal Bi, and the material is assembled through Van der Waals interaction between adjacent Cl layers, so that a rapid diffusion path between ion layers can be realized, thereby promoting reversible redox reaction and increasing the stability of a cycle process, and solving the problems.
The invention provides the following technical scheme:
a preparation method of a battery electrode composite material comprises the following steps:
s1: preparation of CuBTC: ultrasonically dissolving cupric salt in an organic solvent, adding a mixed solution of trimesic acid ultrasonically dissolved in the organic solvent, standing, adding the organic solvent, centrifuging and drying to obtain the CuBTC;
s2: preparing a Cu@C precursor: annealing the CuBTC in an inert atmosphere to obtain the Cu@C precursor;
s3: preparation of flake transition metal oxychloride: dissolving the Cu@C precursor and the transition metal chloride salt in an organic solvent, stirring, performing hydrothermal reaction, and centrifuging to obtain the flaky transition metal oxychloride.
Preferably, the cupric salt in the step S1 is one of cupric nitrate and cupric chloride;
preferably, in the step S1, the mass ratio of the copper nitrate to the trimesic acid is 1-3:1;
preferably, step S1 is carried out for 2-6 hours to prepare the CuBTC;
preferably, the organic solvent in the step S1 is at least one of methanol and ethylene glycol;
preferably, the temperature rising rate of the CuBTC in the step S2 is 2-5 ℃/min, and the annealing temperature is 500-700 ℃;
preferably, the inert atmosphere in the step S2 is one of nitrogen atmosphere, argon atmosphere and helium atmosphere;
preferably, the transition metal chloride salt in the step S3 is trivalent bismuth chloride;
preferably, the flaky transition metal oxychloride in the step S3 is flaky bismuth oxychloride;
preferably, in the step S3, the mass ratio of the Cu@C precursor to the trivalent bismuth chloride is 1:3-5;
preferably, the reaction temperature of the hydrothermal reaction in the step S3 is 100-150 ℃ and the reaction time is 18-24h.
A battery electrode composite material prepared by the preparation method.
Preferably, the battery electrode composite material is a transition metal oxychloride prepared by the preparation method.
More preferably, the battery electrode composite is a sheet-like bismuth oxychloride.
The battery electrode composite material prepared by the method is applied to the field of sodium ion battery materials.
Preferably, the battery electrode composite material is flaky bismuth oxychloride;
more preferably, the flaky bismuth oxychloride, the acetylene black (conductive agent) and the polyvinylidene fluoride (binder) are uniformly mixed according to the mass ratio of 7:2:1, then N-methyl pyrrolidone is added to prepare slurry, the slurry is uniformly coated on a copper foil to prepare a negative electrode, a sodium sheet is used as a positive electrode, a sodium hexafluorophosphate solution with the concentration of 1mol/L is used as an electrolyte, and glass fiber is used as a diaphragm, so that the half cell is assembled.
Compared with the prior art, the battery electrode composite material, the preparation method and the application thereof provided by the invention have the following advantages and beneficial effects:
1) Copper ions and organic ligands are introduced, a metal organic framework is effectively guided and constructed, and then the organic ligands are removed through high-temperature calcination, so that a carbon-coated copper simple substance precursor is formed. The hydrothermal reaction causes the metallic copper to exchange with bismuth ions, and the bismuth trichloride takes the metallic copper as a site to grow flaky bismuth oxychloride in situ;
2) The flaky bismuth oxychloride as an electrode material has a larger surface area, and simultaneously more active sites are exposed, so that more sodium ions can be deintercalated in the charge and discharge process, and a larger capacity is obtained;
3) By enlarging the contact area between the electrode material and the electrolyte, a rapid diffusion path between ion layers is constructed, and the mobility of sodium ions is improved;
4) The synergistic effect of the transition metal oxychlorides contributes to the stability of the battery.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is a schematic diagram of a BiOCl preparation process according to an embodiment of the present invention;
FIG. 2 is a diagram of a BiOCl scanning electron microscope in accordance with an embodiment of the present invention;
FIG. 3 is an XRD pattern for BiOCl in accordance with an embodiment of the present invention;
FIG. 4 is a ratio cycling chart of BiOCl (Cu@C: biCl) according to an embodiment of the invention 3 The mass ratio is 1: 4) The method comprises the steps of carrying out a first treatment on the surface of the
FIG. 5 is a graph showing the cycling performance of BiOCl at a current density of 1.0A/g in accordance with an embodiment of the present invention;
FIG. 6 is a ratio cycling chart of BiOCl (Cu@C: biCl) according to an embodiment of the invention 3 The mass ratio is 1: 3) The method comprises the steps of carrying out a first treatment on the surface of the
FIG. 7 is a graph showing the cycle performance of BiOCl at a current density of 1.0A/g (Cu@C: biCl) according to an embodiment of the present invention 3 The mass ratio is 1: 3).
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The invention is further described below with reference to the drawings and examples.
Embodiment one:
the preparation method of the battery electrode composite material provided by the invention, referring to fig. 1, specifically comprises the following steps:
s1: preparation of CuBTC
1.75g of copper nitrate (Cu (NO) 3 ) 2 ) Dissolving in 50mL of methanol solution and carrying out ultrasonic treatment for half an hour, dissolving 0.875g of trimesic acid (H3 BTC) in 50mL of methanol solution and carrying out ultrasonic treatment for half an hour, mixing the two solutions, standing for 2 hours, centrifuging methanol, and drying to obtain CuBTC;
s2: preparation of Cu@C precursor
Annealing CuBTC at 600 ℃ in nitrogen atmosphere, and heating at a rate of 5 min/DEG C to obtain Cu@C;
s3: preparation of BiOCl
Dissolving Cu@C and BiCl3=1:4 in 100mL of glycol solution, stirring for 30min, transferring into a polytetrafluoroethylene hydrothermal kettle, heating at 120 ℃ for 18h, and centrifuging to obtain BiOCl.
As shown in FIG. 2, from the scanning electron microscope image of BiOCl prepared as described above, the prepared transition metal oxychloride BiOCl has a nano-plate structure, and as shown in FIG. 3, the transition metal oxychloride BiOCl has been successfully grown.
Embodiment two:
the BiOCl prepared in example I was subjected to an electrical property test.
Uniformly mixing BiOCl, acetylene black (conductive agent) and polyvinylidene fluoride (binder) according to a mass ratio of 7:2:1, adding a proper amount of N-methyl pyrrolidone to prepare slurry, uniformly coating the slurry on a copper foil to prepare a negative electrode, using a sodium sheet as a positive electrode, using a sodium hexafluorophosphate solution (a solvent is dimethyl ether) with a concentration of 1mol/L as an electrolyte and using glass fibers as a diaphragm, assembling the semi-battery, and carrying out charge and discharge tests at different current densities.
As shown in fig. 4 and 6, the discharge capacity was 280mAh/g at a current density of 0.1A/g and 150mAh/g at a current density of 5A/g; in FIG. 4, cu@C: biCl 3 The mass ratio is 1:4, a step of; in FIG. 6, cu@C: biCl 3 The mass ratio is 1:3.
as shown in fig. 5 and 7, at a current density of 1A/g, the initial coulomb efficiency is high, the subsequent coulomb efficiency is basically maintained at about 100%, and the specific capacity of 150mAh/g is still maintained after 1000 cycles, which indicates that the material structure is stable, and the specific capacity of the material is high. In FIG. 5, cu@C: biCl 3 The mass ratio is 1:4, a step of; in FIG. 7, cu@C: biCl 3 The mass ratio is 1:3.
the preparation method and the battery electrode composite material prepared by the method provided by the embodiment of the invention, and the battery electrode composite material are applied to batteries, wherein the flaky bismuth oxychloride has larger surface area, larger capacity and high sodium ion mobility, and meanwhile, the stability of the battery is improved through the synergistic effect with the transition metal oxychloride; has the following characteristics: 1) The flaky bismuth oxychloride as an electrode material has a larger surface area, and simultaneously more active sites are exposed, so that more sodium ions can be deintercalated in the charge and discharge process, and a larger capacity is obtained; 2) By enlarging the contact area between the electrode material and the electrolyte, a rapid diffusion path between ion layers is constructed, and the mobility of sodium ions is improved; 3) The synergistic effect of the transition metal oxychlorides contributes to the stability of the battery.
Finally, it should be noted that, within the scope of the present invention, other components, proportions and preparation process parameters are specifically selected to achieve the technical effects of the present invention, so they are not listed one by one. Meanwhile, the above embodiments are only for illustrating the technical solution of the present invention, not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the battery electrode composite material is characterized by comprising the following steps of:
(1) Preparation of CuBTC: ultrasonically dissolving cupric salt in an organic solvent, adding a mixed solution of trimesic acid ultrasonically dissolved in the organic solvent, standing, adding the organic solvent, centrifuging and drying to obtain the CuBTC;
(2) Preparing a Cu@C precursor: annealing the CuBTC in an inert atmosphere to obtain the Cu@C precursor;
(3) Preparing flake transition metal oxychloride: dissolving the Cu@C precursor and transition metal chloride in an organic solvent, stirring, performing hydrothermal reaction, and centrifuging to obtain the flaky transition metal oxychloride;
the transition metal chloride salt is trivalent bismuth chloride, and the flaky transition metal oxychloride is flaky bismuth oxychloride;
the mass ratio of the Cu@C precursor to the trivalent bismuth chloride is 1:3-5.
2. The method for producing a battery electrode composite material according to claim 1, characterized in that: the reaction temperature of the hydrothermal reaction is 100-150 ℃ and the reaction time is 18-24h.
3. The method for producing a battery electrode composite material according to claim 1, characterized in that: the cupric salt is one of copper nitrate and copper chloride, and the mass ratio of the copper nitrate to the trimesic acid is 1-3:1.
4. The method for producing a battery electrode composite material according to claim 1, characterized in that: the CuBTC is prepared by standing for 2-6 hours.
5. The method for producing a battery electrode composite material according to claim 1, characterized in that: the temperature rising rate of the CuBTC during annealing is 2-5 ℃/min, and the annealing temperature is 500-700 ℃.
6. A battery electrode composite produced according to the method of producing a battery electrode composite according to any one of claims 1 to 5.
7. The battery electrode composite of claim 6, wherein: the battery electrode composite material is the flaky bismuth oxychloride, the discharge capacity of the flaky bismuth oxychloride is 280mAh/g under the current density of 0.1A/g, and the discharge capacity of the flaky bismuth oxychloride is 150mAh/g under the current density of 5A/g.
8. Use of the battery electrode composite material according to claim 6 in the field of sodium ion batteries, characterized in that: the battery electrode composite material is the flaky bismuth oxychloride, acetylene black and polyvinylidene fluoride are uniformly mixed according to the mass ratio of 7:2:1, then N-methyl pyrrolidone is added to prepare slurry, the slurry is uniformly smeared on a copper foil to prepare a negative electrode, a sodium sheet is used as a positive electrode, a sodium hexafluorophosphate solution with the concentration of 1mol/L is used as an electrolyte, and glass fiber is used as a diaphragm, so that the half battery is assembled.
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|---|---|---|---|---|
| CN105826085A (en) * | 2016-05-24 | 2016-08-03 | 湘潭大学 | Carbon/bismuth oxychloride super capacitor battery and preparation method thereof |
| CN108383160A (en) * | 2018-04-11 | 2018-08-10 | 湘潭大学 | A kind of preparation method and applications of metallic element doping BiOCl nanometer sheet materials |
| CN113839038A (en) * | 2021-08-12 | 2021-12-24 | 山东大学 | MOF-derived Bi @ C nano composite electrode material and preparation method thereof |
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