CN114976006A - Tin/carbon porous micron cage-shaped composite material and preparation method and application thereof - Google Patents
Tin/carbon porous micron cage-shaped composite material and preparation method and application thereof Download PDFInfo
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001694 spray drying Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000007833 carbon precursor Substances 0.000 claims description 7
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims 1
- 235000003704 aspartic acid Nutrition 0.000 claims 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 238000005054 agglomeration Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 239000004005 microsphere Substances 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- 239000002733 tin-carbon composite material Substances 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 238000005469 granulation Methods 0.000 abstract description 4
- 230000003179 granulation Effects 0.000 abstract description 4
- 230000008595 infiltration Effects 0.000 abstract description 4
- 238000001764 infiltration Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000003763 carbonization Methods 0.000 abstract description 3
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000003917 TEM image Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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- 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
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Abstract
The invention discloses a tin/carbon porous micron cage-shaped composite material and a preparation method and application thereof. The material has the hollow microsphere appearance, the inside of the microsphere is provided with a pore canal communicated with the inside, and the superfine nano tin particles are dispersed in the carbon substrate. The invention adopts a spray drying granulation method to obtain a microsphere precursor, obtains a tin-carbon composite material through high-temperature pyrolysis carbonization and reduction, and obtains an internal pore channel by using a pore-forming agent. The carbon substrate can effectively inhibit the agglomeration growth of the nano tin particles in the preparation and application processes, and the internally communicated pore channel structure is favorable for the infiltration of electrolyte and the diffusion of lithium/sodium ions. When the composite material is used as a lithium ion battery cathode, excellent cycle stability and rate capability are shown.
Description
Technical Field
The invention relates to the field of synthesis of a lithium/sodium ion battery cathode material, in particular to a tin/carbon porous micron cage-shaped composite material, a preparation method thereof and application thereof as a lithium/sodium ion battery cathode.
Background
Lithium ion batteries have become mainstream electrochemical energy storage devices at present due to a plurality of advantages, and the improvement of the performance of the lithium ion batteries has an important promoting effect on social development. Some complementary advantages of sodium ion batteries over lithium ion batteries also make them successful in the commercial phase. By optimizing an electrode material system, the current lithium/sodium ion battery still has a larger capacity improvement space, and related fields are also hot directions for new energy research.
The tin negative electrode has high theoretical specific capacity in lithium/sodium ions, the theoretical lithium storage specific capacity of the tin negative electrode is 994mAh/g, and the theoretical sodium storage specific capacity of the tin negative electrode is 847mAh/g, so that the tin negative electrode has high practical development value. The major impediment to the commercialization of tin as a lithium/sodium ion battery is the large volume change during charging and discharging that leads to particle pulverization, shedding, and ion diffusion kinetics degradation induced by agglomeration. Due to the similarity of the problems of the tin negative electrode in the lithium/sodium ion battery, the reasonable modification method is expected to improve the performance of the tin negative electrode lithium/sodium ion battery. At present, the pulverization problem of a tin cathode is improved by adopting nanocrystallization, and simultaneously, the tin particle agglomeration is inhibited by further compounding a carbon material. However, researchers are troubled by the problem of how to inhibit the agglomeration and growth of tin particles in the preparation process and improve the low ion transmission efficiency caused by the over-thick carbon layer, and meanwhile, the development of a low-cost and high-efficiency material preparation method is also one of the keys of the practical popularization of tin-based negative electrodes.
The invention provides a preparation method of a tin/carbon porous micron cage-shaped composite material and application of the tin/carbon porous micron cage-shaped composite material as a lithium/sodium ion battery cathode material. Uniformly mixing a tin source, a carbon source and a pore-forming agent by a spray drying method, and obtaining the tin/carbon composite material with an internal communicating pore channel by pyrolysis carbonization, reduction and washing. The superfine nano tin particles are uniformly dispersed in the carbon substrate, so that the structural stability of the material is improved; the internal communicating pore channel and the high-conductivity component are beneficial to ion transmission and charge transfer.
Disclosure of Invention
The invention provides a tin/carbon porous micron cage-shaped composite material and a preparation method thereof.
Superfine nano tin particles are uniformly dispersed in the carbon skeleton, and the internally communicated pore channels are favorable for the infiltration of electrolyte, thereby improving the ion diffusion efficiency.
The tin particle size is 3-50nm, preferably 5-10 nm.
The carbon skeleton is doped or undoped amorphous carbon or crystalline carbon, preferably nitrogen-doped amorphous carbon.
The pore structure is created by a pore-forming agent, preferably a soluble salt such as sodium chloride.
The tin/carbon porous micron cage-shaped composite material can be used as a lithium/sodium ion battery negative electrode material.
The preparation method of the tin/carbon porous micron cage-shaped composite material comprises the following steps:
the first step is as follows: dispersing a carbon precursor in deionized water, and adjusting the pH value to completely dissolve the carbon precursor to obtain a solution A; the second step is that: adding a soluble pore-forming agent into the solution A, and stirring and dissolving to obtain a solution B; the third step: adding tin salt into the solution B, and uniformly stirring to obtain a solution or suspension C; the fourth step: carrying out spray drying treatment on the mixture C to obtain powder D; the fifth step: calcining the powder D in a tubular furnace with a specific atmosphere, and naturally cooling to obtain powder E; and a sixth step: and washing the powder E with deionized water to remove the pore-forming agent, carrying out suction filtration, repeating for three times, and carrying out vacuum drying to obtain the product.
In the first step, the carbon precursor is a nitrogen-containing or non-nitrogen-containing carbon source, preferably a nitrogen-containing carbon source such as ethylene diamine tetraacetic acid, and the addition amount of the carbon precursor relative to deionized water is 10-100 g/L.
In the first step, the pH is adjusted to 8-14. The pH regulator is weak acid or weak base, preferably ammonia water.
In the second step, the addition amount of the pore-forming agent relative to the deionized water is 10-200 g/L.
In the third step, the tin salt is stannous chloride, stannic chloride pentahydrate or a combination thereof, preferably stannic chloride pentahydrate; the addition amount of the tin salt relative to the deionized water is 10-100 g/L.
In the fifth step, the adopted protective atmosphere is argon or a hydrogen-argon mixed gas.
The air inlet temperature in the spray drying process is 180-220 ℃, and preferably 210 ℃; the air outlet temperature is 90-110 ℃; the sample injection rate is 20-80sccm, preferably 50 sccm.
The calcining atmosphere is inert atmosphere; the calcination temperature is 500-800 ℃, preferably 700 ℃; the holding time is 1-3h, preferably 2 h.
The invention provides a preparation method of a tin/carbon porous micron cage-shaped composite material, which has the following beneficial effects when used as a cathode of a lithium/sodium ion battery:
1. the carbon substrate and the pore-forming agent particles effectively inhibit the agglomeration of tin particles in the preparation and use processes, and the superfine tin particles relieve the volume expansion, thereby being beneficial to improving the structural stability of the material and improving the ion diffusion efficiency.
2. The carbon skeleton provides a highly conductive network channel.
3. The internal communication channel is beneficial to the diffusion of lithium/sodium ions.
4. When the composite material is used as a lithium ion battery cathode, excellent cycle stability and rate capability are shown.
Drawings
FIG. 1 is an XRD pattern of a tin/carbon porous micron cage composite of example 1;
FIG. 2 is an SEM image of a tin/carbon porous micron cage composite of example 1;
FIG. 3 is a TEM image of the tin/carbon porous micrometer cage composite of example 1;
FIG. 4 is a graph of the cycling performance of the tin/carbon porous micron cage composite of example 1 in a lithium ion battery;
FIG. 5 is a graph showing the cycling performance of the tin/carbon porous micron cage composite of example 1 in a sodium ion battery;
FIG. 6 is an XRD pattern of the tin/carbon porous micron cage composite of example 2;
FIG. 7 is an SEM image of a tin/carbon porous micron cage composite of example 2;
FIG. 8 is a TEM image of the tin/carbon porous micrometer cage composite of example 2;
Detailed Description
The tin/carbon porous micron cage-shaped composite material has the hollow micron sphere shape, the inside of the micron sphere is provided with a pore canal communicated with the inside, and superfine nano tin particles are dispersed in a carbon substrate. The invention adopts a spray drying granulation method to obtain a microsphere precursor, obtains a tin-carbon composite material through high-temperature pyrolysis carbonization and reduction, and obtains an internal pore channel by using a pore-forming agent. The carbon substrate can effectively inhibit the agglomeration growth of the nano tin particles in the preparation and application processes, and the internally communicated pore channel structure is favorable for the infiltration of electrolyte and the diffusion of lithium/sodium ions. When the composite material is used as a lithium ion battery cathode, excellent cycle stability and rate capability are shown.
The invention is further described with reference to the following figures and specific examples.
Example 1
The preparation method of the tin/carbon porous micron cage-shaped composite material comprises the following specific steps:
firstly, dispersing 3.2g of ethylenediamine tetraacetic acid powder into 200ml of deionized water, dropwise adding 5ml of 28% ammonia water, and stirring to completely dissolve the powder; secondly, adding 5g of sodium chloride as a pore-forming agent, and stirring for dissolving; thirdly, adding 3.6g of stannic chloride pentahydrate crystals, and stirring for 1 hour; fourthly, performing spray drying granulation on the mixture obtained in the third step, wherein the air inlet temperature is 210 ℃, the air outlet temperature is over 90 ℃, and the sample injection speed is 50sccm to obtain dry powder; fifthly, calcining the powder in an argon atmosphere at a heating rate of 10 ℃/min and a heat preservation temperature of 700 ℃ for 2h, and naturally cooling; and sixthly, washing the powder obtained in the fifth step with water, performing suction filtration, repeating the steps for three times, and drying the powder in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain a final product.
And (3) carrying out X-ray diffraction analysis and scanning/transmission electron microscope characterization on the product, and matching with a button cell assembled by a metal lithium sheet to carry out charge and discharge performance test. Fig. 1 is an XRD pattern of the product, with the main peak corresponding to the β -Sn phase, demonstrating carbothermal reduction of the tin precursor to elemental tin at high temperatures. The small amount of the hetero-peak corresponds to the tin oxide being completely reduced. A hump appearing around 25 ° at 2 θ corresponds to a carbon (002) peak, indicating that the pyrolyzed carbon is in an amorphous state. FIG. 2 is a morphology of the product under a scanning electron microscope, and it can be seen that the product is a porous cage-like structure of 1-5 μm, which indicates that the pore-forming agent is successfully removed and an open pore is formed, and the pore structure is favorable for the infiltration of the electrolyte and the ion diffusion, and relieves the internal stress generated by volume expansion. Fig. 3 is a morphology diagram of the product under a transmission electron microscope, and it can be seen that interconnected channels form a cage-like structure, fine tin particles are dispersed in a carbon skeleton, and no obvious agglomeration phenomenon of tin particles is observed. Fig. 4 shows the electrochemical cycle test result of the button half cell assembled by the product matching lithium sheet, wherein the figure shows the specific charge capacity and the coulombic efficiency, the charge-discharge voltage range is 0.005-2V, and the charge-discharge current density is 200 mA/g. The first charging specific capacity is 800.5mAh/g, the first coulombic efficiency is 55.4%, the charging specific capacity after 150 cycles is kept at 610.3mAh/g, and the higher specific capacity and the cycling stability of the material are proved. Fig. 5 shows the electrochemical cycle test results of button half cells assembled by matching sodium sheets, showing the specific charge capacity and coulombic efficiency, the charge-discharge voltage range is 0.005-2V, and the charge-discharge current density is 50 mA/g. The first charging specific capacity is 441.1mAh/g, the first coulombic efficiency is 40.5%, and the capacity is maintained to be 312.1mAh/g after 100 cycles.
Example 2
The preparation method of the tin/carbon porous micron cage-shaped composite material comprises the following specific steps:
firstly, dispersing 3.12g of sucrose into 200ml of deionized water, and stirring to completely dissolve powder; secondly, adding 5g of sodium chloride as a pore-forming agent, and stirring for dissolving; thirdly, adding 3.6g of stannic chloride pentahydrate crystals, and stirring for 1 hour; fourthly, performing spray drying granulation on the mixture obtained in the third step, wherein the air inlet temperature is 210 ℃, the air outlet temperature is over 90 ℃, and the sample injection speed is 50sccm to obtain dry powder; fifthly, calcining the powder in an argon atmosphere at a heating rate of 10 ℃/min, keeping the temperature at 700 ℃ for 2h, and naturally cooling; and sixthly, washing the powder obtained in the fifth step with water, performing suction filtration, repeating the steps for three times, and drying the powder in a vacuum oven at the temperature of 60 ℃ for 12 hours to obtain a final product.
And carrying out X-ray diffraction analysis and scanning/transmission electron microscope characterization on the product. Fig. 6 is an XRD pattern of the product, with the main peak corresponding to the β -Sn phase, demonstrating carbothermal reduction of the tin precursor to elemental tin at high temperatures. The intensity of the diffraction peak of tin relative to the amorphous carbon hump is stronger in this example than the product of example 1, indicating that the grain size of tin is larger in this example. Fig. 7 is a topography of the sample under a scanning electron microscope, and it can be seen that the product is a porous microsphere, and the overall topography is similar to that of the product in example 1, but a cluster composed of nanoparticles is visible, which is presumed to be a cluster formed by the agglomeration of tin particles. Fig. 8 is a morphology of the product under a transmission electron microscope, and it can be seen that the product has an interconnected pore structure, the granular sensation of the nano tin is obvious, and larger particles of about 100nm are formed in a local area. As can be seen from the comparison of example 1, different carbon sources have important influence on the morphology of the tin-carbon composite material, and a basis is provided for the morphology control of the tin-carbon composite material.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The tin/carbon porous micron cage-shaped composite material is characterized by comprising nano tin particles and a carbon framework, wherein the carbon framework is of a micron-scale cage-shaped structure, communicated pore channels are formed in the carbon framework, and the nano tin particles are dispersed in the carbon framework.
2. The tin/carbon porous micron cage composite of claim 1, wherein the nano tin particle size is 3-50 nm.
3. The tin/carbon porous micron cage composite of claim 1, wherein the carbon skeleton is doped or undoped amorphous or crystalline carbon.
4. A preparation method of a tin/carbon porous micron cage-shaped composite material is characterized by comprising the following steps:
the first step is as follows: dispersing a carbon precursor in deionized water, and adjusting the pH value to completely dissolve the carbon precursor to obtain a solution A;
the second step is that: adding a soluble pore-forming agent into the solution A, and stirring and dissolving to obtain a solution B;
the third step: adding tin salt into the solution B, and uniformly stirring to obtain a mixture C, wherein the mixture C is a solution or a suspension;
the fourth step: performing spray drying treatment on the mixture C to obtain powder D;
the fifth step: calcining the powder D in a tubular furnace with a specific atmosphere, and naturally cooling to obtain powder E;
and a sixth step: and washing the powder E with deionized water to remove the pore-forming agent, carrying out suction filtration, repeating for a plurality of times, and carrying out vacuum drying to obtain the product of the tin/carbon porous micron cage-shaped composite material.
5. The method for preparing the tin/carbon porous micron cage-shaped composite material according to claim 3, wherein in the first step, the carbon precursor is one or more of sucrose, ethylene diamine tetraacetic acid and aspartic acid.
6. The method for preparing the tin/carbon porous micro-cage composite material according to claim 3, wherein in the first step, the pH regulator used for regulating the pH value is a weak acid or a weak base.
7. The method for preparing the tin/carbon porous micron cage-shaped composite material as claimed in claim 3, wherein in the second step, the pore-forming agent is one or more of sodium chloride, sodium carbonate and sodium bicarbonate.
8. The preparation method of the tin/carbon porous micron cage-shaped composite material according to claim 3, wherein the tin salt used in the third step is one or more of stannous chloride, stannic chloride tetrahydrate and stannic chloride pentahydrate.
9. The method for preparing a tin/carbon porous micron cage composite material as set forth in claim 1, wherein the calcining atmosphere used in the fifth step is an inert atmosphere.
10. Use of a tin/carbon porous micro cage composite according to any of claims 1 to 3, or prepared according to the method of any of claims 4 to 9, as a negative electrode material for lithium or sodium ion batteries.
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| CN102142553A (en) * | 2011-02-12 | 2011-08-03 | 中南大学 | Tin-cobalt-carbon compound material having nanometer/micron structure and preparation method thereof |
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| CN105742602A (en) * | 2016-03-27 | 2016-07-06 | 华南理工大学 | Sn/MoS<2>/C composite material for sodium ion battery negative electrode and preparation method therefor |
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| CN102142553A (en) * | 2011-02-12 | 2011-08-03 | 中南大学 | Tin-cobalt-carbon compound material having nanometer/micron structure and preparation method thereof |
| CN104916829A (en) * | 2015-04-20 | 2015-09-16 | 长春理工大学 | Nitrogen-doped porous nanometer carbon-tin composite lithium ion battery negative electrode material and preparation method thereof |
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