CN111470487A - Preparation method and application of biomass carbon material - Google Patents

Preparation method and application of biomass carbon material Download PDF

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Publication number
CN111470487A
CN111470487A CN202010392650.0A CN202010392650A CN111470487A CN 111470487 A CN111470487 A CN 111470487A CN 202010392650 A CN202010392650 A CN 202010392650A CN 111470487 A CN111470487 A CN 111470487A
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China
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carbon material
biomass carbon
ion battery
sintering
potato starch
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CN202010392650.0A
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高林
王祖静
杨学林
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China Three Gorges University CTGU
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China Three Gorges University CTGU
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/05Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides a preparation method and application of a biomass carbon material. In the production process of potato starch, a large amount of residues are generated after starch is extracted. And (3) taking a certain amount of starch residues, drying in an oven, and sintering and grinding to prepare the spherical biomass carbon material. In addition, the material is activated by strong alkali, and the porous biomass carbon material can be obtained. The material has better electrochemical performance when used as a sodium ion battery and a potassium ion battery. The method is simple and easy to operate, high in repeatability, low in economic cost, environment-friendly and suitable for recycling various biomass residues.

Description

Preparation method and application of biomass carbon material
Technical Field
The invention relates to a sodium ion and potassium ion battery cathode material, in particular to preparation and application of a biomass carbon material, and belongs to the field of energy storage materials and technologies.
Background
Nowadays, the problems of energy shortage and environmental protection have attracted people's high attention. In the industrial production of starch, a large amount of residues are produced, and the main components of the residues are cellulose, lignin, pectin, saccharides and the like. The soluble sugar contained in the lactic acid bacteria is easy to cause fermentation of the lactic acid bacteria to cause sour taste, the longer the storage time is, the larger the acidity is, and the lactic acid bacteria are easy to be polluted by fungi and putrefying bacteria to deteriorate. In order to respond to the national environmental protection requirement, the invention provides a simple and easy-to-operate starch residue treatment method. The invention recycles the sodium ions and the potassium ions to prepare the negative electrode carbon material with better electrochemical performance. Not only well solves the problem of waste residue in the industrial production process of starch, but also provides a new sodium and potassium ion battery cathode material.
Disclosure of Invention
The invention aims to solve the problem of recycling residues in the industrial production process of starch, and the residues are prepared into a biomass carbon material through a certain process, and the biomass carbon material has better electrochemical performance when being applied to negative electrode materials of sodium ion and potassium ion batteries.
The specific synthesis step is that a certain amount of potato starch residues are taken and placed in an oven to be dried for later use. And (3) placing the dried potato starch residues in a corundum boat, and performing two-step sintering in a tube furnace to obtain the spherical biomass carbon material.
The potato starch residue refers to residue generated after starch is extracted in the production process of potato starch.
The sintering comprises two steps, wherein the first step of sintering is to heat up to 200 ℃ at a heating rate of 3 ℃/min in an air environmentoAnd C, pre-oxidizing for 2-6h at the temperature of-260 ℃, and enhancing the shape and structural stability of the carbon material. The second step of sintering is to heat up to 600 ℃ at a heating rate of 3 ℃/min in a nitrogen atmosphereoCalcining at the temperature of between 900 and 1 to 3 hours to convert the potato starch residues into carbon materials and improve the graphitization degree of the carbon materials.
The technical scheme is that dried potato starch residues and a certain amount of strong base are ground, mixed, placed in a corundum boat, calcined in a tubular furnace under the protection of inert gas, washed to be neutral by hydrochloric acid and deionized water, and dried to obtain the porous biomass carbon material. The sintering condition is that the temperature is raised to 600-900 ℃ at the heating rate of 3 ℃/min and calcined for 1-3h under the nitrogen atmosphere.
The present invention uses KOH as an activator. Due to K+Radius ratio of Na+The radius is larger, the pore-forming capability is stronger, and the porous biomass carbon material can be obtained.
The mass ratio of the potato starch residues to the strong alkali is 1: 0.5-1.
The concentration of hydrochloric acid used is 2-5M.
The invention also provides an application of the prepared biomass carbon material in preparation of potassium ion batteries or sodium ion batteries.
The invention recycles potato residue starch residues in the industrial starch production process, prepares the potato residue starch residues into a biomass carbon material used as a negative electrode material of sodium ion and potassium ion batteries, and has the following characteristics:
(1) the preparation method is simple and easy to operate, has strong repeatability and is suitable for large-scale production. Meanwhile, the production cost is low, no by-product is generated in the production process, the production efficiency is high, and the method is environment-friendly.
(2) The preparation method provides a new solution for recycling the starch residue in the industrial starch production process, and is also suitable for recycling other biomass residues.
(3) The biomass carbon material prepared by the method has a spherical or porous shape. The spherical shape has a larger specific surface area, which is beneficial to the contact of the electrolyte and the active substance. The specific surface area of the prepared porous biomass carbon material is further increased through strong alkali corrosion, and meanwhile, the porous structure is also beneficial to ion transmission.
Drawings
FIG. 1 is a graph of the cycle performance of the material prepared in example 1, where A is a sodium ion battery and B is a potassium ion battery.
Fig. 2 is a graph of cycle performance of the material prepared in example 2, a being a sodium ion battery and B being a potassium ion battery. .
Fig. 3 is an XRD pattern of the material prepared in example 3.
FIG. 4 is SEM images of materials prepared in example 3 at different magnification sizes, wherein A is 100 μm, B is 10 μm, and C is 1 μm.
Fig. 5 is a graph of cycle performance of the material prepared in example 3, a being a sodium ion battery and B being a potassium ion battery.
FIG. 6 is a graph of the large current cycling performance of the material prepared in example 3, where A is a sodium ion battery and B is a potassium ion battery.
Fig. 7 is an XRD pattern of the material prepared in example 4.
FIG. 8 is SEM images of materials prepared in example 4 at different magnification sizes, wherein A is 100 μm, B is 10 μm, and C is 1 μm.
Fig. 9 is a graph of cycle performance of the material prepared in example 4, a being a sodium ion battery and B being a potassium ion battery.
FIG. 10 is a graph of the large current cycling performance of the material prepared in example 4, where A is a sodium ion battery and B is a potassium ion battery.
Detailed Description
Example 1
Weighing 2g of dried potato starch residues, flatly paving the dried potato starch residues in a corundum material boat, and putting the corundum material boat into a tube furnace. The biomass carbon material is obtained through two-step sintering. The first step of sintering is heating to 230 ℃ at the heating rate of 3 ℃/min in the air environment, pre-oxidizing for 4h, then the second step of sintering is heating to 700 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphere, calcining for 2h, naturally cooling to room temperature, and grinding to obtain the biomass carbon material. The material is mixed with acetylene black and PVDF according to the mass ratio of 8:1:1 and ground to prepare an electrode plate, and the electrode plate is assembled with metal sodium and metal potassium to form a sodium ion battery and a potassium ion battery to carry out electrochemical performance test. At 100 mAg-1The initial specific capacity of the sodium-ion battery is 238.2 mAh g at the current density of-1The first coulombic efficiency is 32.63%, and the coulombic efficiency is tested after 100 circles of continuous charge and discharge. At 100 mA g-1The initial specific capacity of the potassium ion battery is 110.9mAh g at the current density of (A)-1The first coulombic efficiency is 14.53%, and the capacity has certain attenuation after 100 circles of continuous charge and discharge tests (as shown in figure 1).
Example 2
Weighing 2g of dried potato starch residues, flatly paving the dried potato starch residues in a corundum material boat, and putting the corundum material boat into a tube furnace. The biomass carbon material is obtained through two-step sintering.The first step of sintering is to heat up to 230 ℃ at the heating rate of 3 ℃/min in the air environment, pre-oxidize for 4h, and then the second step of sintering is to heat up to 900 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphereoAnd C, calcining for 2h, naturally cooling to room temperature, and grinding to obtain the biomass carbon material. The material is mixed with acetylene black and PVDF according to the mass ratio of 8:1:1 and ground to prepare an electrode plate, and the electrode plate is assembled with metal sodium and metal potassium to form a sodium ion battery and a potassium ion battery to carry out electrochemical performance test. At 100 mAg-1The initial specific capacity of the sodium-ion battery is 231.5 mAh g at the current density of (A)-1The first coulombic efficiency is 28.17%, and the coulombic efficiency is tested after 100 circles of continuous charge and discharge. At 100 mA g-1The initial specific capacity of the potassium ion battery is 380.0mAh g at the current density of (1)-1The first coulombic efficiency is 13.73%, and after 100 circles of continuous charge and discharge tests, the capacity attenuation is serious, and the specific capacity is about 97 mAh g-1Left and right (as in fig. 2). The sodium ion battery capacity was reduced compared to example 1, and the cycle stability was significantly reduced although the potassium ion battery capacity was improved.
Example 3
Weighing 2g of dried potato starch residues, flatly paving the dried potato starch residues in a corundum material boat, and putting the corundum material boat into a tube furnace. The biomass carbon material is obtained through two-step sintering. The first step of sintering is to heat up to 230 ℃ at the heating rate of 3 ℃/min in the air environment, pre-oxidize for 4h, and then the second step of sintering is to heat up to 800 ℃ at the heating rate of 3 ℃/min in the nitrogen atmosphereoAnd C, calcining for 2h, naturally cooling to room temperature, and grinding to obtain the biomass carbon material. As can be seen by the results of XRD characterization of FIG. 3, the results are shown at 23.68o、42.84oCharacteristic peaks are shown, which correspond to the (002) and (101) crystal planes of carbon. As shown by the SEM characterization result in FIG. 4, the biomass carbon material prepared by the method has micron-sized spherical morphology. The material is mixed with acetylene black and PVDF according to the mass ratio of 8:1:1 and ground to prepare an electrode plate, and the electrode plate is assembled with metal sodium and metal potassium to form a sodium ion battery and a potassium ion battery to carry out electrochemical performance test. At 100 mA g-1At a current density of (a), the initial specific capacity of the sodium ion battery is 307.4 mAh g-1First coulomb effectThe rate is 54.22%, after 100 circles of continuous charge and discharge tests, the specific capacity is 132.6 mAh g-1(see fig. 5). At 100 mA g-1The initial specific capacity of the potassium ion battery is 304.2 mAh g at the current density of (A)-1The first coulombic efficiency is 66.19%, the capacity has certain attenuation after 100 circles of continuous charge and discharge tests, and the specific capacity is about 156.8 mAh g-1Left and right (as in fig. 5). Compared with the embodiment 1 and the embodiment 2, the capacity and the cycle performance of the sodium ion battery and the potassium ion battery are obviously improved. At 1000 mA g-1Under the current density, the initial specific capacity of the sodium-ion battery is 139.7mAh g-1The initial coulombic efficiency is 31.33 percent, and the initial specific capacity of the potassium ion battery is 239.1mAh g-1The first coulombic efficiency was 40.4%.
Example 4
Weighing 2g of dried potato starch residues and 2g of potassium hydroxide, ball-milling at 500r/min for 2h, spreading in a corundum boat, putting the boat in a tube furnace, and heating to 800 ℃ at a heating rate of 3 ℃/min in a nitrogen atmosphereoCalcining for 2h, and naturally cooling to room temperature. Washing with 3M hydrochloric acid solution to remove excessive potassium hydroxide and carbonate generated during reaction, washing with deionized water to neutral, and placing the material at 80 deg.CoAnd C, drying in an oven, and grinding to obtain the porous biomass carbon material. As seen from the results of XRD characterization of FIG. 7, the results are shown in 23.02o、42.94oCharacteristic peaks are shown, corresponding to the (002) and (101) crystal planes of carbon, respectively. As shown by the SEM characterization result of FIG. 8, the biomass carbon material prepared by the method has the morphology of a porous structure. The material is mixed with acetylene black and PVDF according to the mass ratio of 8:1:1 and ground to prepare an electrode plate, and the electrode plate is assembled with metal sodium and metal potassium to form a sodium ion battery and a potassium ion battery to carry out electrochemical performance test. At 100 mA g-1The initial specific capacity of the sodium-ion battery under the current density is 879.7 mAh g-1The first coulombic efficiency is 20.70 percent, and the specific capacity is 173.6 mAh g after 100 circles of continuous charge and discharge tests-1(see fig. 5). At 100 mA g-1The initial specific capacity of the potassium ion battery under the current density is 915.7mAh g-1The first coulombic efficiency is 12.97%, and after 100 circles of continuous charge and discharge tests, the specific capacity is about 150.1 mAhg-1Left and right (as in fig. 9). Compared with the embodiment 3, the first discharge specific capacity of the sodium ion battery and the potassium ion battery is obviously improved, but the first coulombic efficiency is lower, because the porous structure brings larger specific surface area, more SEI films are generated in the reaction process, more irreversible reactions occur, and the first coulombic efficiency is lower. But the capacity and the cycle performance are obviously improved. At 1000 mA g-1The initial specific capacity of the sodium-ion battery is 406.9mAh g under the current density-1The initial coulombic efficiency is 14.5%, and the initial specific capacity of the potassium ion battery is 512.4mAh g-1The first coulombic efficiency was 12.55%. The sodium/potassium ion battery has better cycle stability.

Claims (9)

1. A preparation method of a biomass carbon material is characterized in that potato starch residues are dried and placed in a corundum boat and sintered to obtain the biomass carbon material.
2. The method for producing a biomass carbon material according to claim 1, wherein the potato starch residue is a residue produced after starch extraction in a potato starch production process.
3. The method for preparing biomass carbon material according to claim 1, wherein the sintering comprises 2 steps, the first step sintering is heating to 200-260 ℃ at a heating rate of 3 ℃ min in an air environment, pre-oxidizing for 2-6h, and the second step sintering is heating to 600-900 ℃ at a heating rate of 3 ℃/min in a nitrogen atmosphere, and calcining for 1-3 h.
4. The method for preparing the biomass carbon material according to claim 1, wherein the biomass carbon material is prepared by mixing and grinding potato starch residue and strong base, placing the mixture in a corundum boat for sintering, cleaning the product obtained after sintering to be neutral by hydrochloric acid and deionized water, and drying the product.
5. The method for preparing biomass carbon material according to claim 4, wherein the sintering condition is calcination at a temperature rise rate of 3 ℃/min to 600-900 ℃ for 1-3h under nitrogen atmosphere.
6. The method for producing a biomass carbon material according to claim 4, wherein the strong base comprises sodium hydroxide or potassium hydroxide.
7. The method for producing a biomass carbon material according to claim 4, wherein the mass ratio of the potato starch residue to the strong base is 1: 0.5-1.
8. The method for producing a biomass carbon material according to claim 4, wherein the hydrochloric acid is used at a concentration of 2 to 5M.
9. Use of the biomass carbon material prepared according to any one of claims 1 to 8 for preparing a potassium ion battery or a sodium ion battery.
CN202010392650.0A 2020-05-11 2020-05-11 Preparation method and application of biomass carbon material Pending CN111470487A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112299391A (en) * 2020-10-15 2021-02-02 南京师范大学 Water chestnut derived oxygen-doped carbon material and preparation method and application thereof
CN112436138A (en) * 2020-10-26 2021-03-02 福建海峡石墨烯产业技术研究院有限公司 Ligustrum-derived binderless self-standing carbon foam negative electrode material and preparation method thereof
CN114275761A (en) * 2021-12-22 2022-04-05 中国科学院江西稀土研究院 Carbon material for producing singlet oxygen and preparation method and application thereof
CN116692858A (en) * 2023-04-17 2023-09-05 湖北万润新能源科技股份有限公司 Preparation method and application of sodium ion battery biomass hard carbon anode material

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CN109860594A (en) * 2019-01-18 2019-06-07 三峡大学 A kind of preparation method of starch residue preparation negative electrode material
CN110668418A (en) * 2019-10-16 2020-01-10 张家港博威新能源材料研究所有限公司 Preparation method of hard carbon microspheres with high specific capacitance

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Publication number Priority date Publication date Assignee Title
CN103288080A (en) * 2013-06-14 2013-09-11 中国石油大学(华东) Method for preparing high-mesopore-ratio high-adsorptivity ecological carbon
CN109148883A (en) * 2017-09-26 2019-01-04 中国科学院物理研究所 Anode material of lithium-ion battery and its preparation method and application based on pitch
CN108511204A (en) * 2018-04-02 2018-09-07 张家港博威新能源材料研究所有限公司 A kind of preparation method of the nitrogen co-doped Porous hollow carbosphere of oxygen
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CN110668418A (en) * 2019-10-16 2020-01-10 张家港博威新能源材料研究所有限公司 Preparation method of hard carbon microspheres with high specific capacitance

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112299391A (en) * 2020-10-15 2021-02-02 南京师范大学 Water chestnut derived oxygen-doped carbon material and preparation method and application thereof
CN112436138A (en) * 2020-10-26 2021-03-02 福建海峡石墨烯产业技术研究院有限公司 Ligustrum-derived binderless self-standing carbon foam negative electrode material and preparation method thereof
CN114275761A (en) * 2021-12-22 2022-04-05 中国科学院江西稀土研究院 Carbon material for producing singlet oxygen and preparation method and application thereof
CN116692858A (en) * 2023-04-17 2023-09-05 湖北万润新能源科技股份有限公司 Preparation method and application of sodium ion battery biomass hard carbon anode material
CN116692858B (en) * 2023-04-17 2024-03-15 湖北万润新能源科技股份有限公司 Preparation method and application of sodium ion battery biomass hard carbon anode material

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