CN114420931A - Composite negative electrode material for sodium ion battery and preparation method and application thereof - Google Patents
Composite negative electrode material for sodium ion battery and preparation method and application thereof Download PDFInfo
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- CN114420931A CN114420931A CN202111669362.6A CN202111669362A CN114420931A CN 114420931 A CN114420931 A CN 114420931A CN 202111669362 A CN202111669362 A CN 202111669362A CN 114420931 A CN114420931 A CN 114420931A
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- ion battery
- antimony sulfide
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 56
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims abstract description 80
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 17
- 239000010405 anode material Substances 0.000 claims description 16
- CSNDXHSGSSAWOF-UHFFFAOYSA-L disodium;ethenyl phosphate Chemical compound [Na+].[Na+].[O-]P([O-])(=O)OC=C CSNDXHSGSSAWOF-UHFFFAOYSA-L 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- -1 sodium vinyl borate Chemical compound 0.000 claims description 7
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 125000005619 boric acid group Chemical group 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
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- 238000007599 discharging Methods 0.000 abstract description 9
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- 239000013543 active substance Substances 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 27
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- 239000000463 material Substances 0.000 description 10
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- 238000001878 scanning electron micrograph Methods 0.000 description 8
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- 230000000694 effects Effects 0.000 description 5
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
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- 229910052744 lithium Inorganic materials 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052959 stibnite Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- IHBMMJGTJFPEQY-UHFFFAOYSA-N sulfanylidene(sulfanylidenestibanylsulfanyl)stibane Chemical compound S=[Sb]S[Sb]=S IHBMMJGTJFPEQY-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound 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
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a composite negative electrode material for a sodium ion battery, and a preparation method and application thereof. The composite negative electrode material for the sodium ion battery comprises antimony sulfide and an unsaturated compound. The preparation method comprises the following steps: and mixing antimony sulfide with the unsaturated compound solution, and removing the solvent to obtain the composite negative electrode material for the sodium-ion battery. According to the invention, by utilizing the characteristic that unsaturated double bonds contained in unsaturated compounds can undergo in-situ polymerization in the charging and discharging processes, a protective layer with higher toughness is constructed on the surface of antimony sulfide, and meanwhile, the unsaturated compounds are not dissolved in electrolyte, so that the antimony sulfide active substances can be prevented from being corroded by the electrolyte, and the sodium reversible storage capacity is achieved, and the purposes of prolonging the cycle life of a battery and improving the capacity, energy density and rate capability are achieved.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to a composite negative electrode material for a sodium ion battery, and a preparation method and application thereof.
Background
The lithium ion battery applied in large scale in the market at present can not meet the requirements of people gradually because of the problems of limited resources, high price and the like. Sodium ions have gained attention from researchers in this context. The sodium ion battery has excellent safety performance and good power performance, and can be applied in a larger temperature range. However, graphite, which is widely used in lithium ion batteries, cannot exert its advantages in sodium ion batteries because the radius of sodium ions is larger than that of lithium ions. Therefore, the research of a novel negative electrode material which has good electrochemical performance, high safety performance, economy and environmental protection for the sodium ion battery is the key point of the current research.
Antimony sulfide (Sb)2S3) Is a semiconductor material with excellent photoelectric performance and sodium storage property. In addition, the preparation method has the characteristics of high capacity, simplicity in preparation, low cost and the like, and has a wide application prospect in the field of electrode materials. When used as the cathode material of the sodium ion battery, the antimony sulfide can generate conversion reaction and alloying reaction with sodium, and has a theoretical specific capacity of 946 mAh/g. However, in the process of charging and discharging, antimony sulfide can generate the volume expansion of 364 percent, which causes the pulverization and the falling of materials, and the problems of battery impedance rise, rapid cycle attenuation failure and the like can occur. To solve the above problems, researchers mainly use metal oxide coating, carbon coating, and the like to relieve the volume expansion of antimony sulfide. However, these inorganic coatings also have problems, on the one hand, that these surface-modifying materials are electrochemically inert, and that the coating cannot be broken by volume changes of the active material during electrochemical cycling, resulting in large amounts of active sodium ions being consumed, collapse of the conductive network of the electrode, severe obstruction to sodium ion migration, and finally failure of the battery cycle. On the other hand, the methods have high manufacturing cost and low yield and are difficult to be used for industrial mass production.
CN109768239A discloses a sodium ion battery negative electrode material and a preparation method thereof. The cathode material of the sodium ion battery is a composite material formed by coating antimony sulfide nanowires with a nitrogen-doped carbon layer, and the obtained composite material is used for the sodium ion battery. Firstly, synthesizing antimony sulfide nanowires by a one-step hydrothermal method, then uniformly loading dopamine on the antimony sulfide nanowires through reaction, and finally obtaining the composite material formed by the antimony sulfide nanowires coated by the nitrogen-doped carbon layer through heat treatment.
CN110492074A discloses a method for preparing a carbon fiber/antimony sulfide composite cathode of a lithium ion battery, which can directly use natural stibnite as an electrode active substance and carbon fiber as a conductive matrix, and synthesize a novel cathode material with a carbon fiber substrate coated with nano-scale antimony sulfide by melting.
CN107331842A discloses an antimony sulfide-based negative electrode material with high reversible capacity, and preparation and application thereof. The antimony sulfide-based negative electrode material is Sb2S3-C composite powder material, wherein Sb2S3The antimony sulfide powder is pure antimony sulfide powder and is the main component of a powder material, and accounts for 50-90% of the mass percentage content, and the C is a graphite carbon material and accounts for 10-50% of the mass percentage content; is prepared by ball milling antimony sulfide powder and graphite carbon materials by a dielectric barrier discharge plasma auxiliary high-energy ball milling method.
The three documents are inorganic composite or coating, on one hand, the surface modification materials are electrochemically inert, and the coating layer can not be cracked by enduring the volume change of the active material in the electrochemical cycle process, so that a large amount of active sodium ions are consumed, an electrode conductive network collapses, the migration of the sodium ions is seriously hindered, and finally the battery cycle fails. On the other hand, the methods have high manufacturing cost and low yield and are difficult to be used for industrial mass production.
Therefore, how to improve the electrochemical performance of the antimony sulfide negative electrode material in the sodium ion battery is a technical problem which needs to be solved urgently.
Disclosure of Invention
The invention aims to provide a composite negative electrode material for a sodium-ion battery, and a preparation method and application thereof. According to the invention, by utilizing the characteristic that unsaturated double bonds contained in unsaturated compounds can undergo in-situ polymerization in the charging and discharging processes, a protective layer with higher toughness is constructed on the surface of antimony sulfide, and meanwhile, the unsaturated compounds are not dissolved in electrolyte, so that the antimony sulfide active substances can be prevented from being corroded by the electrolyte, and the sodium reversible storage capacity is achieved, and the purposes of prolonging the cycle life of a battery and improving the capacity, energy density and rate capability are achieved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a composite anode material for a sodium ion battery, comprising antimony sulfide and an unsaturated compound.
In the present invention, the unsaturated compound forms a protective layer on the surface of antimony sulfide through an unsaturated bond.
According to the invention, a protective layer with higher toughness is constructed on the surface of antimony sulfide by utilizing the characteristic that unsaturated double bonds contained in an unsaturated compound can be subjected to in-situ polymerization in the charging and discharging processes, so that the problem of volume expansion of the antimony sulfide can be solved, and the purpose of prolonging the cycle life of a battery is achieved; the unsaturated compound is insoluble in the electrolyte, so that the active material can be effectively protected from being corroded by the electrolyte; the unsaturated compound has the capacity of reversible sodium storage, can provide partial capacity, and effectively improves the energy density of the battery.
In the invention, if a saturated compound is selected, the process that unsaturated double bonds can generate in-situ polymerization in the charging and discharging process cannot be realized, and the formed solid-liquid phase interface film has poor toughness and is easy to crack, so that the capacity of the battery is rapidly reduced.
Preferably, the unsaturated compound includes any one of a sulfonic acid group, a phosphoric acid group, or a boric acid group, or a combination of at least two thereof.
In the invention, the unsaturated compound contains sulfonic acid groups, phosphoric acid groups or boric acid groups, and the special functional groups can obviously improve the mobility of sodium ions and enhance the rate capability of the battery.
Preferably, the unsaturated compound comprises any one of sodium vinyl sulfonate, sodium vinyl phosphate or sodium vinyl borate or a combination of at least two thereof.
Preferably, the mass ratio of the antimony sulfide to the unsaturated compound is 100 (10-80), for example 100:10, 100:15, 100:20, 100:25, 100:30, 100:35, 100:40, 100:45, 100:50, 100:60, 100:70 or 100:80, and preferably 100 (10-45).
In the invention, the mass ratio of antimony sulfide to unsaturated compound is in the range of 100 (10-45), the unsaturated compound can better play a role in an antimony sulfide interface, when the mass ratio is too small, namely the addition amount of the unsaturated compound is too much, the impedance of an electrode is obviously increased, and the playing of antimony sulfide capacity is not facilitated, and when the mass ratio is too large, namely the addition amount of the unsaturated compound is too little, a protective layer formed on the antimony sulfide interface is unstable, and the protective layer is easy to crack in the later period of electrochemical cycle, so that the cycle water-skipping of a battery is caused.
In a second aspect, the present invention provides a method for preparing a composite anode material for a sodium-ion battery according to the first aspect, the method comprising:
and mixing antimony sulfide with the unsaturated compound solution, and removing the solvent to obtain the composite negative electrode material for the sodium-ion battery.
The preparation method provided by the invention is simple to operate, does not need complex procedures, has good effect and low cost, and provides possibility for large-scale application of antimony sulfide in the future.
Preferably, the solvent in the unsaturated compound solution comprises any one of water, ethanol, dimethylformamide, dimethylsulfoxide, tetrahydrofuran or N-methylpyrrolidone or a combination of at least two of them.
Preferably, the method of mixing comprises sonication.
Preferably, the solvent removal method comprises oil bath heating and/or water bath heating.
Preferably, the temperature of the water bath heating is 50-120 ℃, such as 50, 60, 70, 80, 90, 100, 110 or 120.
In a third aspect, the present invention also provides a sodium ion battery comprising the composite anode material for a sodium ion battery according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, by utilizing the characteristic that unsaturated double bonds contained in unsaturated compounds can undergo in-situ polymerization in the charging and discharging processes, a protective layer with higher toughness is constructed on the surface of antimony sulfide, and meanwhile, the unsaturated compounds are not dissolved in electrolyte, so that the antimony sulfide active substances can be prevented from being corroded by the electrolyte, and the sodium reversible storage capacity is achieved, and the purposes of prolonging the cycle life of a battery and improving the capacity, energy density and rate capability are achieved. According to the battery provided by the invention, the lithium removal capacity at 0.05C can reach more than 855.4mAh/g, the first effect can reach more than 67.41%, the reversible capacity after circulation for 200 circles at 0.5C can reach more than 480.6mAh/g, a charge test is carried out under the condition of 0.1C, a discharge test is carried out under 0.1-100C, the rate performance is more than good (the standard is shown in the specification test condition), the lithium removal capacity at 0.05C can reach more than 876.6mAh/g after the mass ratio of antimony sulfide and unsaturated compounds is further limited, the first effect can reach more than 68.78%, and the reversible capacity after circulation for 200 circles at 0.5C can reach more than 591.1 mAh/g.
Drawings
Fig. 1 is an SEM image of the negative electrode material for a sodium ion battery provided in comparative example 1.
Fig. 2 is an SEM image of the negative electrode material for sodium ion battery provided in example 1.
Fig. 3 is a TEM image of the anode material for sodium-ion battery provided in comparative example 1.
Fig. 4 is a TEM image of the negative electrode material for a sodium ion battery provided in example 1.
Fig. 5 is a graph comparing the first charge and discharge curves of the batteries provided in example 1 and comparative example 1.
Fig. 6 is a graph comparing rate performance of the batteries provided in example 1 and comparative example 1.
Fig. 7 is a graph comparing the cycle performance of the batteries provided in example 1 and comparative example 1.
Fig. 8 is an SEM image of the negative electrode after 100 cycles of the battery provided in comparative example 1.
Fig. 9 is an SEM image of the negative electrode after 100 cycles of the battery provided in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a composite negative electrode material for a sodium ion battery, the composite negative electrode material for the sodium ion battery is an antimony sulfide nanorod and sodium vinylsulfonate (sodium vinylsulfonate forms a protective layer on the antimony sulfide nanorod through an unsaturated bond), and the mass ratio of the antimony sulfide to the sodium vinylsulfonate is 100: 10.
The preparation method of the negative electrode material comprises the following steps:
dissolving 2g of sodium vinylsulfonate in 50ml of deionized water to form a sodium vinylsulfonate solution, then adding 20g of antimony sulfide nanorods into the solution, fully mixing, ultrasonically dispersing in an ultrasonic cleaning instrument for 2 hours, placing the ultrasonically treated solution in a water bath kettle, continuously stirring and heating at the temperature of 100 ℃ until the solvent is completely volatilized, and obtaining the composite cathode material for the sodium ion battery.
Example 2
The difference between this example and example 1 is that in this example, the mass ratio of antimony sulfide to sodium vinylsulfonate is 100:20, and the mass of sodium vinylsulfonate in the preparation method is 4 g.
The remaining preparation methods and parameters were in accordance with example 1.
Example 3
The difference between this example and example 1 is that in this example, the mass ratio of antimony sulfide to sodium vinylsulfonate is 100:40, and the mass of sodium vinylsulfonate in the preparation method is 4 g.
The remaining preparation methods and parameters were in accordance with example 1.
Example 4
The embodiment provides a composite negative electrode material for a sodium ion battery, wherein the composite negative electrode material for the sodium ion battery comprises antimony sulfide nanorods and sodium vinylphosphate (the sodium vinylphosphate forms a protective layer on the antimony sulfide nanorods through unsaturated bonds), and the mass ratio of the antimony sulfide to the sodium vinylphosphate is 100: 10.
The remaining preparation methods and parameters were in accordance with example 1.
Example 5
The difference between the present example and example 4 is that in the present example, the mass ratio of antimony sulfide to sodium vinylphosphate is 100:20, and in the preparation method, the mass of sodium vinylphosphate is 4 g.
The remaining preparation methods and parameters were in accordance with example 1.
Example 6
The difference between the present example and example 4 is that in the present example, the mass ratio of antimony sulfide to sodium vinylphosphate is 100:40, and in the preparation method, the mass of sodium vinylphosphate is 8 g.
The remaining preparation methods and parameters were in accordance with example 1.
Example 7
The embodiment provides a composite negative electrode material for a sodium ion battery, wherein the composite negative electrode material for the sodium ion battery comprises antimony sulfide nanorods and sodium vinyl borate (the sodium vinyl borate forms a protective layer on the antimony sulfide nanorods through unsaturated bonds), and the mass ratio of the antimony sulfide to the sodium vinyl borate is 100: 20;
the remaining preparation and parameters were in accordance with example 1 (preparation with a sodium vinylborate mass of 4 g).
Example 8
The difference between this example and example 1 is that in this example, the mass ratio of antimony sulfide to sodium vinylsulfonate is 100:50, and the mass of sodium vinylsulfonate in the preparation method is 10 g.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The difference between the comparative example and the example 1 is that the antimony sulfide nano-rod is directly used as the cathode material in the comparative example.
Fig. 1 shows an SEM image of the negative electrode material for sodium ion battery provided in comparative example 1, and fig. 2 shows an SEM image of the negative electrode material for sodium ion battery provided in example 1, and it can be seen from fig. 1 and 2 that the composite negative electrode material in the present invention does not destroy the morphology and structure of antimony sulfide, and is uniformly dispersed without agglomeration, compared to pure antimony sulfide in comparative example 1.
Fig. 3 shows a TEM image of the anode material for sodium ion battery provided in comparative example 1, fig. 4 shows a TEM image of the anode material for sodium ion battery provided in example 1, and as can be seen from fig. 3 and fig. 4, the anode material in example 1 is coated with a uniform and continuous protective layer of unsaturated compound (sodium vinylsulfonate) with a length of about 20nm on the surface of antimony sulfide to form an unsaturated compound/antimony sulfide composite anode material, and the unsaturated compound is insoluble in the electrolyte, can stably exist in the circulation process, and plays a role of protecting the electrode material.
Fig. 5 shows a comparison graph of the first charge and discharge curves of the batteries provided in example 1 and comparative example 1, and it can be seen from fig. 5 that the first coulombic efficiency of the antimony sulfide negative electrode half-cell provided in comparative example 1 is only 62.73% lower and the reversible capacity is only 821.3mAh/g, compared with the battery provided in example 1, the first coulombic efficiency and the charge and discharge capacity are improved, the first coulombic efficiency of the composite negative electrode half-cell reaches 72.34% at the maximum and the discharge capacity reaches 955.7mAh/g, which indicates that the unsaturated compound compounded with antimony sulfide can participate in the formation of an SEI film and inhibit the sodium consumption during the first charge and discharge process, thereby improving the first coulombic efficiency of the battery.
Fig. 6 shows a comparison of rate performance of the batteries provided in example 1 and comparative example 1, and it can be seen from fig. 6 that the rate performance of the antimony sulfide composite negative electrode provided in example 1 is significantly improved, which is related to the fact that the special functional group contained in the unsaturated compound can improve the sodium conductivity of the SEI film.
Fig. 7 shows a comparison graph of cycle performance of the batteries provided in example 1 and comparative example 1, and it can be seen from fig. 7 that the long-term cycle performance of the battery provided in example 1 is significantly improved, the cycle fading of the antimony sulfide electrode not compounded by the unsaturated compound in comparative example 1 is significant, and the capacity of the battery is reduced to 148mAh/g after 100 times of charging and discharging, compared with the case that the antimony sulfide electrode of example 1 is cycled smoothly, and the capacity of 591.1mAh/g after 300 times of cycling still shows that the unsaturated compound coating layer can effectively inhibit the capacity fading.
Fig. 8 shows an SEM image of the negative electrode of the battery provided in comparative example 1 after 100 cycles, fig. 9 shows an SEM image of the negative electrode of the battery provided in example 1 after 100 cycles, and as can be seen from fig. 8 and 9, the antimony sulfide compounded with unsaturated compound in comparative example 1 after 100 cycles has deposited a very thick and loose surface film on the surface, and the rod-like morphology of the antimony sulfide is not substantially seen, but the antimony sulfide compounded with unsaturated compound in example 1 has not substantially changed in morphology after 300 cycles, and the deposited surface film is not thick, which indicates that the surface SEI film of the antimony sulfide compounded with unsaturated compound is unstable, and is continuously destroyed, grown and dropped during long-term cycling, resulting in surface film, and simultaneously, the material is pulverized and cracked because the formed thick SEI film cannot meet the requirement of expansion of the antimony sulfide, antimony sulfide compounded by unsaturated compounds obviously improves the stability and toughness of an SEI film, and plays a role in protecting the material from being corroded by electrolyte and inhibiting the volume expansion of the material.
Comparative example 2
This comparative example differs from example 1 in that sodium vinyl sulfonate is replaced by sodium alkyl sulfonate in this comparison.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 3
The negative electrode material comprises an antimony sulfide nanorod inner core and a carbon coating layer coated on the surface of the inner core.
The preparation method of the negative electrode material comprises the following steps:
adding a proper amount of antimony sulfide into a solution of trihydroxymethyl aminomethane, carrying out ultrasonic treatment for 30 minutes, adding polydopamine, continuously stirring for 3 hours, then carrying out centrifugal drying, and sintering the obtained sample for 2 hours at 500 ℃ in an argon atmosphere to obtain the carbon-coated antimony sulfide material.
The negative electrode materials for sodium ion batteries provided in examples 1 to 8 and comparative examples 1 to 3, sodium carboxymethylcellulose, and acetylene black were thoroughly and uniformly mixed at a ratio of 70:15:15 to prepare an electrode paste, and the electrode paste was applied to a copper foil current collector (commercially available), dried, and used at 2MPa/cm2Pressing under the pressure of the pressure, cutting, and drying for 16h under the vacuum condition at the temperature of 120 ℃; and assembling the prepared composite electrode into a half cell by taking metal sodium as a counter electrode.
The cells provided in examples 1-8 and comparative examples 1-3 were subjected to electrochemical performance tests under the following test conditions:
wherein the test conditions of the first reversible capacity (delithiation capacity) and the first coulombic efficiency are 0.05C; the test condition of reversible capacity (delithiation capacity) after 100 cycles of cycling was 0.5C; the test conditions of the rate capability are as follows: the charging test is carried out under the condition of 0.1C, the discharging test is carried out under the condition of 0.1-100C, if the ratio of the test result to the reversible capacity is more than or equal to 70%, the result is marked as 'excellent', if the ratio of the test result to the reversible capacity is more than or equal to 50%, the result is marked as 'good', if the ratio of the test result to the reversible capacity is less than 50%, the result is marked as 'poor', and the result is shown in table 1.
TABLE 1
From the data results of example 1 and example 8, it is understood that the mass ratio of antimony sulfide to sodium vinylsulfonate is too small, that is, the battery impedance is significantly increased due to the addition of the sodium vinylsulfonate in an excessive amount, which affects the exertion of the battery capacity.
From the data results of the embodiment 1 and the comparative example 1, the cathode material provided by the invention has the advantages of high coulombic efficiency for the first time, good rate capability and long cycle period compared with antimony sulfide cathode material without any treatment.
From the data of example 1 and comparative example 2, it is clear that the use of saturated compounds is significantly less stable than the use of unsaturated compounds.
From the data results of example 1 and comparative example 3, it is known that the treatment of antimony sulfide by conventional carbon coating means is difficult to achieve the purposes of increasing the energy density of the battery and prolonging the service life of the battery.
In conclusion, the invention utilizes the characteristic that unsaturated double bonds contained in unsaturated compounds can generate in-situ polymerization in the charging and discharging processes, a protective layer with higher toughness is constructed on the surface of antimony sulfide, and meanwhile, the unsaturated compounds are not dissolved in electrolyte, so that antimony sulfide active substances can be prevented from being eroded by the electrolyte, and the antimony sulfide protective layer has the capability of reversibly storing sodium, and the purposes of prolonging the cycle life of a battery and improving the capacity, energy density and rate capability are achieved. According to the battery provided by the invention, the lithium removal capacity at 0.05C can reach more than 855.4mAh/g, the first effect can reach more than 67.41%, the reversible capacity after circulation for 200 circles at 0.5C can reach more than 480.6mAh/g, a charge test is carried out under the condition of 0.1C, a discharge test is carried out under 0.1-100C, the rate performance is more than good (the standard is shown in the specification test condition), the lithium removal capacity at 0.05C can reach more than 876.6mAh/g after the mass ratio of antimony sulfide and unsaturated compounds is further limited, the first effect can reach more than 68.78%, and the reversible capacity after circulation for 200 circles at 0.5C can reach more than 591.1 mAh/g.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The composite negative electrode material for the sodium-ion battery is characterized by comprising antimony sulfide and an unsaturated compound.
2. The composite anode material for a sodium-ion battery according to claim 1, characterized in that the unsaturated compound includes any one of a sulfonic acid group, a phosphoric acid group, or a boric acid group, or a combination of at least two thereof.
3. The composite anode material for a sodium-ion battery according to claim 1 or 2, wherein the unsaturated compound comprises any one of sodium vinyl sulfonate, sodium vinyl phosphate, or sodium vinyl borate, or a combination of at least two thereof.
4. The composite negative electrode material for the sodium-ion battery as claimed in any one of claims 1 to 3, wherein the mass ratio of the antimony sulfide to the unsaturated compound is 100 (10-80), preferably 100 (10-45).
5. A method for preparing a composite anode material for a sodium-ion battery according to any one of claims 1 to 4, characterized in that the preparation method comprises:
and mixing antimony sulfide with the unsaturated compound solution, and removing the solvent to obtain the composite negative electrode material for the sodium-ion battery.
6. The method for preparing the composite anode material for the sodium-ion battery according to claim 5, wherein the solvent in the unsaturated compound solution comprises any one or a combination of at least two of water, ethanol, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, and N-methylpyrrolidone.
7. The method for preparing a composite anode material for a sodium-ion battery according to claim 5 or 6, wherein the mixing method comprises ultrasonication.
8. The method for producing the composite anode material for sodium-ion batteries according to any one of claims 5 to 7, characterized in that the method for removing the solvent comprises oil bath heating and/or water bath heating.
9. The preparation method of the composite anode material for the sodium-ion battery as claimed in claim 8, wherein the temperature of water bath heating is 50-120 ℃.
10. A sodium-ion battery comprising the composite anode material for a sodium-ion battery according to any one of claims 1 to 4.
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| JP2015187985A (en) * | 2014-03-12 | 2015-10-29 | 三菱化学株式会社 | Active material for nonaqueous secondary battery negative electrodes, negative electrode arranged by use thereof, and nonaqueous secondary battery |
| CN105932236A (en) * | 2016-05-09 | 2016-09-07 | 河海大学 | Coating and modifying method for electrode material of lithium ion battery |
| CN113651359A (en) * | 2021-03-31 | 2021-11-16 | 江苏大学 | Preparation method and application of antimony sulfide nanorod |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015187985A (en) * | 2014-03-12 | 2015-10-29 | 三菱化学株式会社 | Active material for nonaqueous secondary battery negative electrodes, negative electrode arranged by use thereof, and nonaqueous secondary battery |
| CN105932236A (en) * | 2016-05-09 | 2016-09-07 | 河海大学 | Coating and modifying method for electrode material of lithium ion battery |
| CN113651359A (en) * | 2021-03-31 | 2021-11-16 | 江苏大学 | Preparation method and application of antimony sulfide nanorod |
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