CN117393728A - High-performance bismuth/hard carbon composite negative electrode material of sodium ion battery - Google Patents
High-performance bismuth/hard carbon composite negative electrode material of sodium ion battery Download PDFInfo
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- CN117393728A CN117393728A CN202311480176.7A CN202311480176A CN117393728A CN 117393728 A CN117393728 A CN 117393728A CN 202311480176 A CN202311480176 A CN 202311480176A CN 117393728 A CN117393728 A CN 117393728A
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- bismuth
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- sodium
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 141
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 title claims description 10
- 239000002245 particle Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 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 abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000001238 wet grinding Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 19
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 16
- 239000002482 conductive additive Substances 0.000 claims description 15
- 239000003273 ketjen black Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 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 claims description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 abstract description 8
- 238000005056 compaction Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 25
- 239000011859 microparticle Substances 0.000 description 11
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000002077 nanosphere Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OLDOGSBTACEZFS-UHFFFAOYSA-N [C].[Bi] Chemical compound [C].[Bi] OLDOGSBTACEZFS-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
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- H—ELECTRICITY
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention discloses a preparation method and application of a bismuth/hard carbon composite anode material, wherein the bismuth in the bismuth/hard carbon composite anode material is 5-80 wt%, micron-sized bismuth particles and hard carbon powder are directly mixed, wet-milled and dried in the preparation process, the bismuth/hard carbon composite anode material effectively solves the problem of capacity rapid attenuation of the bismuth material due to volume expansion effect in the sodium storage electrochemical process, and simultaneously solves the key problems of low compaction density, poor multiplying power performance and the like of commercial hard carbon anodes. The bismuth/hard carbon composite material has the comprehensive properties of high mass specific capacity, high volume specific capacity, high multiplying power and long cycle when being used as a negative electrode of a sodium ion battery. In addition, the material has wide sources, simple preparation method and easy mass production, is used as a high-load sodium ion battery anode material, and shows more excellent comprehensive electrochemical performance than hard carbon and bismuth materials.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a high-performance bismuth/hard carbon composite anode material of a sodium ion battery.
Background
Lithium ion batteries with high energy density and long endurance have been widely used in the fields of consumer electronics, smart grids, aerospace, etc., however, the application of lithium resources in large-scale energy storage scenes is limited due to the disadvantages of scarce lithium resources and high cost. Thus, there is a need to develop new electrochemical energy storage technologies.
Sodium and lithium have similar physical and chemical properties, and are rich in reserves and low in cost. However, the radius of sodium ion isAbout 1.5 times the radius of lithium ions, so the deintercalation of sodium ions in the electrode material exacerbates the destruction of the material structure, making maintaining the stability of the material structure more challenging. Accordingly, researchers have been working on developing low-cost, high-performance sodium storage anode materials.
At present, the main research of the negative electrode material of the sodium ion battery is focused on carbon-based materials, transition metal oxides, alloy-type materials and the like. Alloy-type negative electrode materials (e.g., sb, sn, bi) are attracting attention because of their abundant resources, high theoretical specific capacities, and suitable redox reaction potentials. Wherein, bismuth has the advantages of high theoretical specific capacity (385 mAh g-1), proper voltage platform, reversible alloying, dealloying reaction and the like. Bismuth has several key problems when used as a negative electrode material for sodium ion batteries. First,: based on the reaction mechanism of alloy and dealloying, bismuth can generate continuous structural crushing and reagglomeration in the electrochemical circulation process to cause huge volume expansion (-330%), the crushed bismuth particles can lose contact, and then the bismuth is separated from a current collector to form dead bismuth, so that electron transmission is blocked, and secondly, the bismuth particles are crushed to enable the bismuth particles to expose new surfaces and continuously generate a solid electrolyte interface film, sodium ions are repeatedly consumed, and finally, the rapid capacity decay is shown.
Aiming at the problems, the main modification strategies at present comprise nanocrystallization of materials, nanocarbon coating and the like, so that the volume expansion of bismuth is relieved, the conductivity of the bismuth is improved, and the cycle life of a battery is prolonged. The literature 'Integrating Bi@C Nanospheres in Porous Hard Carbon Frameworks for Ultrafast Sodium Storage' (adv. Mater.2022,34,2202673) discloses a composite material which is characterized in that bismuth nanospheres with an average diameter of 140nm are coated with a carbon layer with a thickness of about 2nm and uniformly distributed on porous carbon nanorods by synthesizing bismuth nanospheres coated with carbon and further distributing the bismuth nanospheres in the porous carbon. The composite material shows good electrochemical performance in sodium ion battery tests, but the preparation method of the nano bismuth and carbon coated composite material is complex and high in cost, and the nano bismuth and electrolyte can undergo serious side reaction to cause low initial coulomb efficiency (52.4%), so that the nano bismuth and carbon coated composite material is difficult to be applied commercially. Patent CN113130873a discloses a bismuth-carbon composite material coated by porous bismuth and an in-situ carbon layer, which shows higher specific sodium storage capacity, excellent rate capability and ultra-long cycling stability, but the magnesium powder used by the composite material has high cost and high requirement on equipment, and does not have the prospect of low-cost commercial mass production.
Based on the above consideration, the development of the cathode material which has the advantages of simple preparation method, green pollution-free property, mass production, high specific capacity under the condition of high load and excellent cycle stability and can be used for the bismuth-based commercialization of sodium ion batteries is significant for the development of sodium ion energy storage devices.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a high-performance bismuth/hard carbon composite anode material for a sodium ion battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
the bismuth/hard carbon composite material comprises 5-80wt.% of bismuth;
the preparation method of the bismuth/hard carbon composite material comprises the following steps:
1) Mixing micron-sized bismuth particles with massive hard carbon, adding absolute ethyl alcohol as a wet grinding solvent, and wet grinding for 8-12 hours at a rotating speed of 100-500 rpm;
2) And collecting powder and drying to obtain the bismuth/hard carbon composite material.
As a possible embodiment, further, the micron-sized bismuth particles have a size of 5 to 20 μm and the bulk hard carbon has a size of 1 to 10 μm.
Further, the compacted density of the bismuth/hard carbon composite material is 1.12-3.12g/cm 3 。
As a preferred embodiment, the bismuth is preferably present in the bismuth/hard carbon composite material in an amount of 20 to 60wt.%.
As a preferred embodiment, step 1) is preferably wet-milled for 10 hours at a speed of 200 rpm.
The bismuth/hard carbon composite material is applied to sodium ion batteries as a negative electrode material. The specific application method of the bismuth/hard carbon composite material as the negative electrode material comprises the following steps:
mixing bismuth/hard carbon composite material, conductive additive and binder according to the ratio of 90:5:5, taking deionized water as dispersing agent, and uniformly coating the prepared slurry on aluminum foil to be used as an electrode plate.
As one possible embodiment, the sodium ion battery further comprises a negative electrode made of bismuth/hard carbon composite material, the counter electrode is metallic sodium, the electrolyte is an ether electrolyte, and the battery is assembled in an argon glove box.
As one possible embodiment, further, the conductive additive is ketjen black (KJB); the binder is a mixture of sodium carboxymethyl cellulose (CMC) and Styrene Butadiene Rubber (SBR);
the electrolyte is prepared by dissolving sodium salt electrolyte in ether solvents, wherein the sodium salt electrolyte is one or more of sodium hexafluorophosphate, sodium perchlorate and sodium tetrafluoroborate; the ether solvent is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
Compared with the prior art, the invention has the following beneficial effects:
(1) The bismuth/hard carbon composite material prepared by the invention effectively overcomes the scientific problems that partial bismuth is deactivated and the material is separated from a current collector due to volume expansion caused by continuous crushing and reagglomeration in the bismuth alloy/dealloying process, and finally the capacity is rapidly attenuated; meanwhile, the key problems of low compaction density, poor multiplying power performance and the like of the commercial hard carbon cathode are solved. Compared with the conventionally used means such as bismuth nano particles, nano carbon coating and the like, the nano-scale anode material has serious side reaction with electrolyte to reduce the first coulomb efficiency, as shown in figure 1, under the condition of equivalent reversible capacity, the first coulomb efficiency of nano bismuth is 88.5 percent, which is lower than 92.3 percent of micro bismuth, and the compaction density of nano bismuth is 4.29g/cm 3 5.57g/cm below micron bismuth 3 . The invention directly adopts the micron bismuth as an active component, and the micron bismuth is directly compounded with the hard carbon negative electrode to manufacture the expansion buffer zone, so that the overall volume expansion rate of the electrode slice is greatly reduced, and the enhanced comprehensive electrochemical performance including mass specific capacity, volume specific capacity, high rate performance and cycle stability is shown.
(2) The bismuth/hard carbon composite material has remarkable breakthrough in key technical indexes: the compaction density of the composite anode reaches 1.12-3.12g/cm 3 1.07g/cm higher than the bulk hard carbon 3 . In addition, the bismuth/hard carbon composite material has excellent volume specific capacity, and the volume specific capacities of Bi20HC80, bi40HC60, bi60HC40 and Bi80HC20 of the bismuth/hard carbon composite material are respectively 302mAh/cm 3 、422mAh/cm 3 、595mAh/cm 3 、956mAh/cm 3 Higher than the bulk hard carbon (279 mAh/cm) 3 )。
(3) The preparation method of the bismuth/hard carbon composite material can prepare the bismuth/hard carbon composite material with high performance through simple ball milling treatment, has short process flow, simple operation and low processing cost, remarkably improves the production efficiency,high yield and easy realization of large-scale production. Wherein, when the bismuth accounts for 20 to 60 weight percent of the bismuth/hard carbon composite material, the initial area specific capacities of Bi20HC80, bi40HC60 and Bi60HC40 are respectively 0.67mAh/cm under the current density of 1A/g 2 、1.03mAh/cm 2 、1.34mAh/cm 2 The capacity retention rates after 1800 circles of stable circulation are 100%, 100% and 98.4% respectively; and when the bismuth accounts for 40wt.% of the bismuth/hard carbon composite material, the bismuth/hard carbon composite material can stably circulate for 2000 circles under the current density of 1A/g, and the area specific capacity is still 1.03mAh/cm 2 The performance is optimal and is far higher than that of pure bismuth microparticles (0.14 mAh/cm 2 ) And a hard carbon negative electrode (0.41 mAh/cm) 2 )。
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings that are required to be used in the description of the embodiments will be briefly described below. It will be apparent that the embodiments described below are only some, but not all, embodiments of the invention. All other embodiments according to these embodiments are within the scope of the invention, as a person of ordinary skill in the art would obtain without undue burden.
FIG. 1 is a graph of the first charge and discharge curves for the micro bismuth of comparative example 2 and the nano bismuth material of comparative example 3 at a current density of 0.1A/g;
FIG. 2 is a mass specific capacity chart of the preferred composite ratio Bi40HC60 of example 4 for 10 turns at different ball milling speeds of 0.2A/g current density;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a cross-section of an electrode sheet of examples 3-6 and comparative examples 1-2;
FIG. 4 is a graph of compaction density data for examples 1-6 and comparative example 1;
FIG. 5 shows the rate performance at different current densities for examples 3-6 and comparative examples 1-2; (ordinate is mass specific capacity)
FIG. 6 is the volumetric capacity corresponding to examples 3-6 and comparative examples 1-2 at different current densities; (the ordinate is the volume specific capacity)
FIG. 7 shows the cycle performance at a current density of 1A/g for examples 3-6 and comparative examples 1-2. (ordinate is area specific capacity)
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a bismuth/hard carbon composite material, wherein the bismuth accounts for 5-80wt.% of the bismuth/hard carbon composite material. The preparation method of the bismuth/hard carbon composite material comprises the following steps:
1) Mixing micron-sized bismuth particles with massive hard carbon, adding absolute ethyl alcohol as a wet grinding solvent, and wet grinding for 8-12h at a rotating speed of 100-500 rpm. In the ball milling process, the ball milling rotating speed and time are very critical, and if the rotating speed is too high, the materials can be broken, and the first coulomb efficiency and the performance of the composite electrode can be reduced; if the ball milling time is too long, bismuth can be melted (melting point 271.5 ℃) to agglomerate, so that the dispersibility of the composite material is reduced; if the ball milling rotation speed is too small or the time is short, the mixture is difficult to be fully and uniformly mixed.
2) Collecting powder and drying to obtain bismuth/hard carbon composite material; the compacted density of the bismuth/hard carbon composite material is 1.12-3.12g/cm 3 。
Wherein, the micron-sized bismuth particles have a size of 5-20 mu m, and the block-shaped hard carbon has a size of 1-10 mu m.
The invention also provides application of the bismuth/hard carbon composite material in a negative electrode material of a sodium ion battery, the bismuth/hard carbon composite material, a conductive additive and a binder are mixed according to the proportion of 90:5:5, deionized water is used as a dispersing agent, the prepared slurry is uniformly coated on an aluminum foil to be used as an electrode plate, a counter electrode is sodium metal, an electrolyte is a conventional ether electrolyte, and the battery is assembled in an argon glove box.
Wherein the conductive additive is ketjen black (KJB), the binder is a mixture of sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR), and the electrolyte is prepared by dissolving sodium salt electrolyte in an ether solvent.
The sodium salt electrolyte is one or more of sodium hexafluorophosphate, sodium perchlorate and sodium tetrafluoroborate;
the ether solvent is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
Example 1:
mixing 5wt.% of bismuth microparticles and 95wt.% of blocky hard carbon according to a mass ratio, performing wet milling treatment at a rotating speed of 200rpm for 10 hours, wherein a wet milling solvent is absolute ethyl alcohol, and drying and collecting to obtain the bismuth hard carbon composite material. A compacted density of 1.12g/cm 3 This was designated as Bi5HC95.
Mixing Bi5HC95, a conductive additive (KJB of Keqin black), a binder (a mixture of sodium carboxymethylcellulose CMC and styrene butadiene rubber SBR) according to a ratio of 90:5:5, taking deionized water as a dispersing agent, uniformly coating the prepared slurry on an aluminum foil to serve as an electrode plate, wherein the loading capacity of the electrode plate is 5-6 mg/cm 2 The counter electrode is sodium metal, the electrolyte is conventional ether electrolyte, and the test is carried out after the battery is assembled in an argon glove box.
Example 2:
mixing 10wt.% of bismuth microparticles and 90wt.% of blocky hard carbon according to a mass ratio, performing wet milling treatment at a rotating speed of 200rpm for 10 hours, wherein a wet milling solvent is absolute ethyl alcohol, and drying and collecting to obtain the bismuth hard carbon composite material. A compacted density of 1.18g/cm 3 This was designated as Bi10HC90.
Mixing Bi10HC90, a conductive additive (KJB of Keqin black), a binder (a mixture of sodium carboxymethylcellulose CMC and styrene butadiene rubber SBR) according to a ratio of 90:5:5, taking deionized water as a dispersing agent, uniformly coating the prepared slurry on an aluminum foil to serve as an electrode plate, wherein the loading capacity of the electrode plate is 5-6 mg/cm 2 The counter electrode is sodium metal, the electrolyte is conventional ether electrolyte, and the test is carried out after the battery is assembled in an argon glove box.
Example 3:
20wt.%And mixing the bismuth microparticles with 80wt.% of blocky hard carbon according to the mass ratio, performing wet milling treatment at the rotating speed of 200rpm for 10 hours, wherein the wet milling solvent is absolute ethyl alcohol, and drying and collecting to obtain the bismuth hard carbon composite material. A compacted density of 1.29g/cm 3 This was designated as Bi20HC80.
Mixing Bi20HC80, a conductive additive (KJB of Keqin black), a binder (a mixture of sodium carboxymethylcellulose CMC and styrene butadiene rubber SBR) according to a ratio of 90:5:5, taking deionized water as a dispersing agent, uniformly coating the prepared slurry on an aluminum foil to serve as an electrode plate, wherein the loading capacity of the electrode plate is 5-6 mg/cm 2 The counter electrode is sodium metal, the electrolyte is conventional ether electrolyte, and the test is carried out after the battery is assembled in an argon glove box.
Example 4:
mixing 40wt.% of bismuth microparticles and 60wt.% of blocky hard carbon according to a mass ratio, performing wet milling treatment at a rotating speed of 200rpm for 10 hours, wherein a wet milling solvent is absolute ethyl alcohol, and drying and collecting to obtain the bismuth hard carbon composite material. A compacted density of 1.63g/cm 3 This was designated as Bi40HC60.
Mixing Bi40HC60, a conductive additive (KJB of Keqin black), a binder (a mixture of sodium carboxymethylcellulose CMC and styrene butadiene rubber SBR) according to a ratio of 90:5:5, taking deionized water as a dispersing agent, uniformly coating the prepared slurry on an aluminum foil to serve as an electrode plate, wherein the loading capacity of the electrode plate is 5-6 mg/cm 2 The counter electrode is sodium metal, the electrolyte is conventional ether electrolyte, and the test is carried out after the battery is assembled in an argon glove box.
Example 5:
mixing 60wt.% of bismuth microparticles and 40wt.% of massive hard carbon according to a mass ratio, performing wet milling treatment at a rotating speed of 200rpm for 10 hours, wherein a wet milling solvent is absolute ethyl alcohol, and drying and collecting to obtain the bismuth hard carbon composite material. A compacted density of 2.15g/cm 3 This was designated as Bi60HC40.
Mixing Bi60HC40, conductive additive (KJB black Ketjen), binder (mixture of CMC and SBR) at a ratio of 90:5:5, and uniformly coating the obtained slurry on aluminum foil with deionized water as dispersing agentIs an electrode plate with the loading capacity of 5-6 mg/cm 2 The counter electrode is sodium metal, the electrolyte is conventional ether electrolyte, and the test is carried out after the battery is assembled in an argon glove box.
Example 6:
mixing 80wt.% of bismuth microparticles and 20wt.% of blocky hard carbon according to a mass ratio, performing wet milling treatment at a rotating speed of 200rpm for 10 hours, wherein a wet milling solvent is absolute ethyl alcohol, and drying and collecting to obtain the bismuth hard carbon composite material. A compacted density of 3.12g/cm 3 This was designated as Bi80HC20.
Mixing Bi80HC20, a conductive additive (KJB of Keqin black), a binder (a mixture of sodium carboxymethylcellulose CMC and styrene butadiene rubber SBR) according to a ratio of 90:5:5, taking deionized water as a dispersing agent, uniformly coating the prepared slurry on an aluminum foil to serve as an electrode plate, wherein the loading capacity of the electrode plate is 5-6 mg/cm 2 The counter electrode is sodium metal, the electrolyte is conventional ether electrolyte, and the test is carried out after the battery is assembled in an argon glove box.
Comparative example 1:
and (3) carrying out wet grinding treatment on the hard carbon for 10 hours at the most preferable rotating speed of 200rpm, wherein the wet grinding solvent is absolute ethyl alcohol, and drying and collecting to obtain the hard carbon powder material. A compacted density of 1.07g/cm 3 。
Mixing hard carbon and a conductive additive (KJB of Keqin black) in a ratio of 90:5:5, using deionized water as a dispersing agent, uniformly coating the prepared slurry on an aluminum foil to serve as an electrode plate, wherein the loading amount of the electrode plate is 5-6 mg/cm 2 The counter electrode is sodium metal, the electrolyte is conventional ether electrolyte, and the test is carried out after the battery is assembled in an argon glove box.
Comparative example 2:
and carrying out wet milling treatment on the bismuth microparticles for 10 hours at the most preferred rotating speed of 200rpm, wherein the wet milling solvent is absolute ethyl alcohol, and drying and collecting the bismuth microparticles to obtain the bismuth micropowder material. A compacted density of 5.57g/cm 3 。
The micron bismuth, conductive additive (Keqin black KJB), binder (sodium carboxymethylcellulose CMC and styrene butadiene rubber)SBR mixture) is mixed according to the proportion of 90:5:5, deionized water is used as a dispersing agent, the prepared slurry is uniformly coated on aluminum foil to be used as an electrode plate, and the loading capacity of the electrode plate is 5-6 mg/cm 2 The counter electrode is sodium metal, the electrolyte is conventional ether electrolyte, and the test is carried out after the battery is assembled in an argon glove box.
Comparative example 3:
and (3) carrying out wet milling treatment on bismuth nano (50 nm) particles for 10 hours at the most preferred rotating speed of 200rpm, wherein a wet milling solvent is absolute ethyl alcohol, and drying and collecting the bismuth nano (50 nm) particles to obtain the nano bismuth powder material. The compacted density was 4.29g/cm 3 。
Mixing nano bismuth and a conductive additive (KJB of Keqin black) in a ratio of 90:5:5, using deionized water as a dispersing agent, uniformly coating the prepared slurry on an aluminum foil to serve as an electrode plate, wherein the loading amount of the electrode plate is 5-6 mg/cm 2 The counter electrode is sodium metal, the electrolyte is conventional ether electrolyte, and the test is carried out after the battery is assembled in an argon glove box.
Fig. 1 is a graph of the first charge and discharge curves corresponding to the micro bismuth of comparative example 2 and the nano bismuth material of comparative example 3 at a current density of 0.1A/g. As can be seen from the graph, the specific discharge capacities of the micro bismuth and the nano bismuth are 413mAh/g and 427mAh/g respectively, and the specific charge capacities are 381mAh/g and 378mAh/g respectively, which indicate that the nano bismuth causes serious side reaction in the primary electrochemical reaction process to cause larger irreversible capacity loss, so that the primary coulomb efficiency (88.5%) of the nano bismuth is lower than that of the micro bismuth (92.3%).
FIG. 2 is a graph showing the mass specific capacity of the preferred composite ratio Bi40HC60 of example 4 for the first 10 rounds at different ball milling speeds of 0.2A/g current density. As can be seen from the graph, after ball milling treatment of 200rmp and 600rmp, the initial coulombic efficiencies of Bi40HC60 are 88.6% and 73.9%, respectively, and the reversible capacities are 308.8mAh/g and 260.7mAh/g, respectively. The results show that: the ball milling rotation speed has a large influence on the performance of the composite material, and the excessive rotation speed can lead to material breakage and reduce the first coulomb efficiency and the reversible capacity of the composite electrode, so that the preferable ball milling rotation speed is 200rmp.
FIG. 3 is a Scanning Electron Microscope (SEM) image of a cross section of an electrode sheet of examples 3-6 and comparative examples 1-2. From the figure, bismuth microparticles are uniformly distributed in the middle of the massive hard carbon, and the overall density of the electrode plate is remarkably improved.
FIG. 4 is a graph of the compaction density data for examples 1-6 and comparative example 1. The results show that: after the composite is compounded, the compacted density of the bismuth/hard carbon composite material reaches 1.12-3.12g/cm 3 1.07g/cm higher than hard carbon 3 . Therefore, the invention effectively solves the problem of low commercial hard carbon compaction density by adjusting the content of bismuth in the bismuth/hard carbon composite material.
Fig. 5 shows the rate performance at different current densities for examples 3-6 and comparative examples 1-2. It can be seen that: the bismuth hard carbon composite material exhibits excellent rate capability, particularly the more preferred example 3 (Bi 40HC 60) still has a high mass specific capacity of 83mAh/g at a current density of 2A/g, much higher than the hard carbon of comparative example 1 (44 mAh/g) and bismuth of comparative example 2 (65 mAh/g).
FIG. 6 shows the volumetric capacities of examples 3-6 and comparative examples 1-2 at different current densities. It can be seen that: the advantages of the bismuth/hard carbon composite material in terms of volume specific capacity are further reflected, compared with the hard carbon, the bismuth/hard carbon composite material remarkably improves the volume specific capacity of the material under high multiplying power, and particularly, the volume specific capacities of Bi20HC80, bi40HC60, bi60HC40 and Bi80HC20 of the bismuth/hard carbon composite material are respectively 302mAh/cm 3 ，422mAh/cm 3 ，595mAh/cm 3 ，956mAh/cm 3 Higher than the bulk hard carbon (279 mAh/cm) 3 )。
FIG. 7 shows the cycle performance at a current density of 1A/g for examples 3-6 and comparative examples 1-2. It can be seen that: comparative example 1 Bi20HC80, bi40HC60, bi60HC40, bi80HC20, comparative example 2 bismuth had initial area specific capacities of 0.41mAh/cm, respectively 2 、0.67mAh/cm 2 、1.03mAh/cm 2 、1.34mAh/cm 2 、1.74mAh/cm 2 、1.89mAh/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the After 1800 cycles of stabilization, the capacity retention was 100%, 98.4%, 59.5%, 7.6%, respectively. Wherein, comparative example 1 hard carbon groupThe prepared battery has better capacity retention rate, but has lower initial area specific capacity and poorer battery performance. Therefore, based on the comprehensive consideration of the cycle stability and the initial area specific capacity, the performance of 20-60wt.% of bismuth in the bismuth/hard carbon composite material is superior to that of comparative examples 1-2 and Bi80HC20; wherein, the bismuth has the best performance when the bismuth accounts for 40wt.% of the bismuth/hard carbon composite material, and the bismuth/hard carbon composite material still has 1.03mAh/cm after 2000 circles of stabilization circulation 2 Is much higher than the hard carbon anode of comparative example 1 (0.41 mAh/cm 2 ) And pure bismuth microparticles of comparative example 2 (0.14 mAh/cm 2 ). The result shows that the addition of the hard carbon effectively relieves the problem of rapid decay of the circulation capacity caused by volume expansion of bismuth in the charge and discharge processes. And the mass percentage of the hard carbon is very critical, if the mass percentage is too large, the specific capacity of the bismuth/hard carbon composite material cannot be effectively improved; if the ratio is too small, the cycle stability of the bismuth/hard carbon composite anode is deteriorated.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. The bismuth/hard carbon composite material is characterized in that bismuth accounts for 5-80wt.% of the bismuth/hard carbon composite material;
the preparation method of the bismuth/hard carbon composite material comprises the following steps:
1) Mixing micron-sized bismuth particles with massive hard carbon, adding absolute ethyl alcohol as a wet grinding solvent, and wet grinding for 8-12 hours at a rotating speed of 100-500 rpm;
2) And collecting powder and drying to obtain the bismuth/hard carbon composite material.
2. The bismuth/hard carbon composite material according to claim 1, wherein the micron-sized bismuth particles are 5-20 μm in size and the bulk hard carbon particles are 1-10 μm in size.
3. The bismuth/hard carbon composite material according to claim 1, wherein the bismuth accounts for 20-60wt.% of the bismuth/hard carbon composite material.
4. The bismuth/hard carbon composite material according to claim 1, wherein the compacted density of the bismuth/hard carbon composite material is 1.12-3.12g/cm 3 。
5. A bismuth/hard carbon composite material according to claim 1, characterized in that step 1) is wet-milled for 10 hours at a rotational speed of 200 rpm.
6. Use of the bismuth/hard carbon composite material as claimed in any one of claims 1 to 5 as negative electrode material in sodium ion batteries.
7. The use according to claim 6, wherein the bismuth/hard carbon composite material is used as a negative electrode material in the following specific application method:
mixing bismuth/hard carbon composite material, conductive additive and binder according to the ratio of 90:5:5, taking deionized water as dispersing agent, and uniformly coating the prepared slurry on aluminum foil to be used as an electrode plate.
8. The use according to claim 7, wherein the sodium ion battery comprises a negative electrode made of bismuth/hard carbon composite material, the counter electrode is metallic sodium, the electrolyte is an ether electrolyte, and the battery is assembled in an argon glove box.
9. The use according to claim 8, wherein the conductive additive is ketjen black; the binder is a mixture of sodium carboxymethyl cellulose and styrene-butadiene rubber;
the electrolyte is prepared by dissolving sodium salt electrolyte in an ether solvent;
wherein, the sodium salt electrolyte is one or more of sodium hexafluorophosphate, sodium perchlorate and sodium tetrafluoroborate; the ether solvent is one or more of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
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