WO2022166282A1 - 一种富氢碳材料的制备方法及应用于锂-钠-钾储能 - Google Patents

一种富氢碳材料的制备方法及应用于锂-钠-钾储能 Download PDF

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WO2022166282A1
WO2022166282A1 PCT/CN2021/128186 CN2021128186W WO2022166282A1 WO 2022166282 A1 WO2022166282 A1 WO 2022166282A1 CN 2021128186 W CN2021128186 W CN 2021128186W WO 2022166282 A1 WO2022166282 A1 WO 2022166282A1
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hydrogen
carbon material
rich carbon
sodium
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连加彪
王娟
高克拉
谢立夫
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江苏大学
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of inorganic nanomaterials and energy storage, and relates to hydrogen-rich carbon materials, in particular to a preparation method of a hydrogen-rich carbon negative electrode material and its application to lithium-sodium-potassium energy storage.
  • Alkali metal (lithium/sodium/potassium) ion capacitors as a combination of alkali metal ion batteries and supercapacitors, combine the high energy density of alkali metal (lithium/sodium/potassium) ion batteries with the high power density and ultra-long length of supercapacitors The cycle life well meets the requirements for a new generation of energy storage devices.
  • Electrode materials are one of the key elements that determine the electrochemical performance of energy storage devices. Because of its good electrical conductivity, high thermal stability, and good layered structure, carbon materials are suitable for the insertion and extraction of metal ions, and are widely used in negative electrodes of batteries and capacitors, such as: graphene, carbon nanotubes, porous carbon, etc. . The actual specific capacitance and energy density of pure carbon electrode materials are low, and the cycle stability is poor, which limits the further application and development of carbon materials in energy storage devices. In recent years, a variety of methods have been developed to improve the electrochemical performance of carbon materials. Among them, heteroatom doping is considered to be an effective strategy to increase electronic conductivity, surface area and active sites, but the doping process is complex and difficult to achieve The precise control of the preparation process is relatively complicated.
  • the present invention provides a preparation method of hydrogen-rich carbon material.
  • a preparation method of hydrogen-rich carbon material comprising the steps:
  • the carbon source is dissolved in deionized water to prepare a solution with a mass fraction of 2 to 10%, marked as solution A, wherein the carbon source is sodium alginate, sodium carboxymethyl cellulose or bio-oil;
  • solution B The catalyst is dissolved in deionized water to prepare a solution with a mass fraction of 1 to 5%, marked as solution B, wherein the catalyst is ferric chloride, zinc chloride or sodium chloride;
  • the dried product is carbonized at 600 ⁇ 1000°C for 1 ⁇ 5h in an inert atmosphere, and then pickled to get it.
  • the freeze-drying described in step C has a temperature of -100 to -20° C. and a freeze-drying time of 12 to 72 hours.
  • the inert gas in step D is argon or nitrogen.
  • the solution used is a hydrochloric acid solution or a sulfuric acid solution with a mass fraction of 30%.
  • the equipment used is a tube furnace or a box furnace, and the heating rate is 2-15°C ⁇ min -1 .
  • the hydrogen-rich carbon material prepared according to the method of the present invention is used in the field of lithium/sodium/potassium ion batteries or capacitors, but is not limited to the above fields.
  • a lithium ion supercapacitor with high energy and high power density comprising a positive electrode sheet, a negative electrode sheet, a diaphragm, a gasket, a gasket and an electrolyte
  • the positive electrode sheet is Ketjen conductive carbon black
  • the negative electrode sheet is made of negative electrode material through It is formed by pre-lithiation
  • the electrolyte is 1M LiPF 6 .
  • the negative electrode sheet is coated with a negative electrode slurry composed of a negative electrode active material, a conductive agent, a dispersant and a binder in a mass ratio of 8:1:1 on the surface of the copper sheet.
  • the negative electrode active material is a hydrogen-rich carbon material
  • the conductive agent is Ketjenblack EC-600JD
  • the dispersant is nitrogen methyl pyrrolidone (NMP)
  • the binder is an oily bond agent polyvinylidene fluoride (PVDF).
  • the pre-lithiation is to assemble the above-mentioned negative electrode material into a 2032 button battery, and under the potential window of 0.01-3V, pre-lithiation is performed for ten turns at a current density of 100 mA/g to obtain a negative electrode sheet.
  • the above-mentioned negative electrode sheet and positive electrode sheet are assembled into a full-cell device with lithium hexafluorophosphate as the electrolyte.
  • the potential window of 0.01 to 4.5 V the cyclic voltammetry curves are measured at different scanning rates, and the rate performance and cycle performance are tested under the current density. .
  • the hydrogen-rich carbon material prepared by the invention has good application prospects in lithium/sodium/potassium ion batteries and lithium/sodium/potassium ion capacitors, and the hydrogen-rich carbon material is used in lithium ion capacitors (LIC) and sodium ion capacitors. Both have high energy/power densities (LIC: 151.2Wh kg -1 /28.4kW kg -1 ; SIC: 100.5Wh kg -1 /18.6kW kg -1 ) as ion capacitors (SICs), and have excellent rate and cycle performance. It can be used as the negative electrode material of alkali metal capacitor energy storage device.
  • the hydrogen-rich carbon material refers to a carbon material containing a large amount of hydrogen, which is a proper term in the field and belongs to a clear description.
  • the energy storage mechanism of hydrogen-rich carbon materials taking lithium storage as an example, the sp 2 hybrid carbon connected to hydrogen becomes sp 3 hybrid carbon for lithium storage. This process is reversible, and the reaction mechanism is as follows:
  • the choice of carbon source will affect the hydrogen content of the final product, and the hydrogen content will affect the lithium/sodium/potassium storage properties of hydrogen-rich carbon materials; the calcination temperature will affect the hydrogen content of the final product, and the hydrogen content will affect the Li/Na/K storage properties of hydrogen-carbon materials.
  • the invention prepares the polymer precursor into a hydrogen-rich carbon material by a self-template method, does not need doping, has simple reaction conditions, uses a cheap solvent, is non-toxic and harmless, meets the requirements of environmental friendliness, and has extremely wide application prospects.
  • the synthesized hydrogen-rich carbon material itself has large disorder and specific surface area, provides more active sites, and exhibits excellent reversible specific capacity, rate capability and cycling performance.
  • the hydrogen-rich carbon material prepared by the present invention exhibits excellent energy/power density and long cycle life, which is beneficial to meet practical demands.
  • Fig. 1 Scanning electron microscope picture (SEM) of the hydrogen-rich carbon material prepared in Example 1;
  • Fig. 2 Transmission electron microscope picture (TEM) of the hydrogen-rich carbon material prepared in Example 1;
  • FIG. 1 Cycling stability diagram of the hydrogen-rich carbon materials prepared in Example 1 assembled into lithium-ion capacitors and sodium-ion capacitors.
  • a preparation method of hydrogen-rich carbon material comprising the steps:
  • solution A Under continuous magnetic stirring, 2 g of the polymeric precursor sodium alginate (SA) was dissolved in 100 mL of deionized water (DI) to form an aqueous solution with a mass fraction of 2%, marked as solution A;
  • solution B Dissolve 1 g of anhydrous ferric chloride FeCl 3 in 100 mL of deionized water to form an aqueous solution with a mass fraction of 1%, marked as solution B;
  • solution A is slowly added to solution B to obtain cross-linked iron (IA) microgel beads, and the washed IA hydrogel beads are freeze-dried to evaporate water by using a freeze dryer ;
  • HCVD hydrogen-rich carbon nanowires
  • HCNW-1 The sample is labeled as HCNW-1, and its microstructure is shown in Figures 1 and 2.
  • Figures 4-6 are the FTIR, MAS-ss-NMR, and EA spectra of the samples, respectively. The results show that the HCNW samples contain carbon, hydrogen and oxygen elements.
  • the prepared HCNW-1 hydrogen-rich carbon material, conductive agent and binder were made into electrodes at 8:1:1, and assembled with lithium sheets to form a half-cell for performance testing. Its capacity at current densities of 0.1, 0.25, 0.5, 1.0 and 2.5A/g are 1144.2, 952.2, 752, 621.3 and 471.8mAh/g, respectively; and after 3000 cycles at 1.0A/g current density, it can reach 94.2 % capacity retention with excellent rate and cycling performance.
  • the prepared HCNW-1 hydrogen-rich carbon material, conductive agent and binder were made into electrodes in an 8:1:1 ratio, and were assembled with sodium sheets to form a half-cell for performance testing. Its capacities at current densities of 0.1, 0.25, 0.5, 1.0 and 2.5 A/g were 362.5, 286.2, 241.4, 203.7, and 145.9 mAh/g, respectively; and 3000 cycles were carried out at current densities of 1.0 A/g, A capacity retention of 89.75% can be achieved with excellent rate and cycling performance, as shown in Figure 7.
  • the prepared HCNW-1 was pre-lithium/sodiumized to make a lithium/sodium ion capacitor, and the performance was tested. Both have high energy density/power density (Li-ion capacitor: 151.2Wh/kg/28.4kW/kg; Na-ion capacitor: 100.5Wh/kg/18.6kW/kg). After 3000 cycles at a current density of 1.0A/g, the lithium ion capacitor (LIC) has a capacity retention rate of 82.16%, and the sodium ion capacitor (SIC) has a capacity retention rate of 83% under the same conditions, and has a higher The Coulombic efficiency of , and the performance stability during the cycle are better, as shown in Figure 8.
  • a preparation method of hydrogen-rich carbon material comprising the steps:
  • solution A Under continuous magnetic stirring, 2 g of the polymeric precursor sodium alginate (SA) was dissolved in 100 mL of deionized water (DI) to form an aqueous solution with a mass fraction of 2%, marked as solution A;
  • solution B Dissolve 1.5 g of anhydrous ferric chloride FeCl 3 in 100 mL of deionized water to form an aqueous solution with a mass fraction of 1.5%, marked as solution B;
  • solution A is slowly added to solution B to obtain cross-linked iron (IA) microgel beads, and the washed IA hydrogel beads are freeze-dried to evaporate water by using a freeze dryer ;
  • the freeze-dried product was carbonized in a horizontal tube furnace under Ar atmosphere for 2 hours, and the carbonization temperature was 700° C.
  • the product was treated with 1M hydrochloric acid (30%) to remove the catalyst to obtain hydrogen-rich carbon nanowires (HCNW ).
  • the sample is labeled HCNW-1.5.
  • the HCNW-1.5 hydrogen-rich carbon material prepared in this example was made into an electrode with a conductive agent and a binder in a ratio of 8:1:1, and was assembled with a lithium sheet to form a half-cell for performance testing.
  • the reversible capacity at 0.1 A/g current density is 781.3 mAh/g.
  • a preparation method of hydrogen-rich carbon material comprising the steps:
  • solution A Under continuous magnetic stirring, 2 g of the polymeric precursor sodium alginate (SA) was dissolved in 100 mL of deionized water (DI) to form an aqueous solution with a mass fraction of 2%, marked as solution A;
  • solution B Dissolve 2 g of anhydrous ferric chloride FeCl 3 in 100 mL of deionized water to form an aqueous solution with a mass fraction of 2%, marked as solution B;
  • solution A is slowly added to solution B to obtain cross-linked iron (IA) microgel beads, and the washed IA hydrogel beads are freeze-dried to evaporate water by using a freeze dryer ;
  • the freeze-dried product was carbonized in a horizontal tube furnace under Ar atmosphere for 2 hours, and the carbonization temperature was 800° C.
  • the product was treated with 1M hydrochloric acid (30%) to remove the catalyst to obtain hydrogen-rich carbon nanowires (HCNW ).
  • the sample is labeled HCNW-2.
  • the elemental analysis (EA) of Figure 6 shows that the HCNW samples obtained in the three examples all contain three elements, H, C, and O, and the H/C atomic ratios of the three HCNW samples are all about 0.5, while the O/C ratios of the three HCNW samples are all about 0.5.
  • the atomic ratio (O content) increases with the concentration of Fe 3+ .
  • the HCNW-2 hydrogen-rich carbon material prepared in this example was made into an electrode with a conductive agent and a binder in a ratio of 8:1:1, and was assembled with a lithium sheet to form a half-cell for performance testing.
  • the reversible capacity at 0.1 A/g current density is 669.9 mAh/g.
  • a preparation method of hydrogen-rich carbon material comprising the steps:
  • solution A Under continuous magnetic stirring, dissolve 2 g of the polymeric precursor sodium carboxymethyl cellulose (CMC) in 100 mL of deionized water (DI) to form an aqueous solution with a mass fraction of 2%, marked as solution A;
  • solution B Dissolve 1 g of anhydrous ferric chloride FeCl 3 in 100 mL of deionized water to form an aqueous solution with a mass fraction of 1%, marked as solution B;
  • solution A was slowly added to solution B to obtain cross-linked iron carboxymethyl cellulose microgel beads, and the washed hydrogel beads were freeze-dried by using a freeze dryer to evaporate water ;
  • the freeze-dried product was carbonized in a horizontal tube furnace under Ar atmosphere for 2.5 hours, and the carbonization temperature was 700° C.
  • the product was treated with 1M hydrochloric acid (30%) to remove the catalyst to obtain a porous hydrogen-rich carbon material.
  • the porous hydrogen-rich carbon material prepared in this example was made into an electrode with a conductive agent and a binder in a ratio of 8:1:1, and was assembled with a sodium sheet to form a half-cell for electrochemical performance testing. 10,000 cycles were carried out at a current density of 2.5 A/g, achieving a capacity retention of 97.1% with excellent rate and cycling performance.
  • the porous hydrogen-rich carbon material prepared in this example was pre-lithiated/sodiumized to form a sodium ion capacitor, and the performance test showed a high energy density/power density (122Wh/kg/17.6kW/kg). After 10,000 cycles at a current density of 1.0 A/g, the capacity retention was 95.7%, with high Coulombic efficiency and cycle stability.

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Abstract

涉及无机纳米材料和储能技术领域，提供一种富氢碳负极材料的制备方法，包括：碳源溶于去离子水中配制成质量分数为2～10％的溶液，标记为溶液A；催化剂溶解在去离子水配制成质量分数为1～5％的溶液，标记为溶液B；将A溶液滴加到B溶液中，搅拌下充分反应后，洗涤、冻干；干燥产物于惰性气氛中600～1000℃碳化1～5h，酸洗，即得。以自模板法将聚合物前驱体制备成富氢碳材料，无需掺杂，反应条件简单，使用的溶剂价格便宜，无毒无害，合成的富氢碳材料本身具有较大的无序度和比表面积，提供更多的活性位点，表现出优异的可逆比容量、倍率性能、循环性能和长循环寿命，有利于满足实际需求。

Description

一种富氢碳材料的制备方法及应用于锂-钠-钾储能 技术领域
本发明属于无机纳米材料和储能技术领域，涉及富氢碳材料，尤其涉及一种富氢碳负极材料的制备方法及应用于锂-钠-钾储能。
背景技术
面对能源枯竭和环境污染带来的压力，人类开始将目光放到新能源的开发与利用上，其中能源的储存是不可或缺的环节，开发出高能量密度和高功率密度的电化学储能系统成为迫切且严峻的问题。二次电池如锂离子电池、钠离子电池等具有能量密度高、环境友好等特点；超级电容器具有功率密度高、充放电时间短、循环寿命长等特点，这两种储能器件均在实际应用中备受关注。
碱金属(锂/钠/钾)离子电容器作为碱金属离子电池和超级电容器的结合体，兼具碱金属(锂/钠/钾)离子电池的高能量密度和超级电容器的高功率密度和超长循环寿命，很好地满足了对新一代储能器件的要求。
电极材料是决定储能器件的电化学性能的关键要素之一。碳材料因为其导电性好，热稳定性高，具有良好的层状结构，适合金属离子的嵌入和脱出，广泛应用于电池和电容器的负极材料，如：石墨烯，碳纳米管，多孔碳等。单纯的碳电极材料的实际比电容和能量密度较低，循环稳定性差，限制了碳材料在储能器件中的进一步应用和发展。近年来，已开发出多种改善碳材料电化学性能的方法，其中，杂原子掺杂被认为是增加电子传导性、表面积及活性位点的有效策略，但掺杂过程复杂且难以实现对结构的精准控制，制备工艺相对复杂。
寻找一种制备方法简单、成本低廉、结构稳定的新型富氢碳材料，具有十分重要的意义。
发明内容
针对碳材料制备方法繁琐及作为电极材料的能量密度低和循环稳定性差的问题，本发明提供一种富氢碳材料的制备方法。
技术方案
一种富氢碳材料的制备方法，包括如下步骤：
A.碳源溶于去离子水中配制成质量分数为2～10％的溶液,标记为溶液A，其中所述碳源为海藻酸钠、羧甲基纤维素钠或生物油；
B.催化剂溶解在去离子水配制成质量分数为1～5％的溶液,标记为溶液B，其中所述催化剂为氯化铁、氯化锌或氯化钠；
C.将A溶液滴加到B溶液中，搅拌下充分反应后，洗涤、冻干；
D.干燥产物于惰性气氛中600～1000℃碳化1～5h，酸洗，即得。
本发明较优公开例中，步骤C中所述冻干，其温度-100～-20℃，冻干时间12～72h。
本发明较优公开例中，步骤D中所述惰性气体为氩气或氮气。
本发明较优公开例中，步骤D中所述酸洗，所用的溶液为质量分数为30％的盐酸溶液或硫酸溶液。
本发明较优公开例中，步骤D中所述碳化，所用设备为管式炉或箱式炉，升温速率为2～15℃·min -1。
根据本发明所述方法制备得到的富氢碳材料，应用于锂/钠/钾离子电池或电容器领域，但又不限于上述领域。
一种高能量和高功率密度的锂离子超级电容器，包括正极片、负极片、隔膜、垫片、垫圈及电解液，所述正极片为科琴导电炭黑，所述负极片由负极材料经过预锂化而成，所述电解液为1M LiPF 6。
进一步的，所述负极片是在铜片表面涂覆由负极活性材料、导电剂、分散剂及粘结剂按质量比为8:1:1组成的负极浆料。其中，所述负极活性材料为富氢碳材料；所述导电剂为科琴导电炭黑Ketjenblack EC-600JD；所述分散剂为氮甲基吡咯烷酮(NMP)；所述粘结剂为油性粘结剂聚偏氟乙烯(PVDF)。
进一步的，所述预锂化是将上述负极材料组装成2032纽扣电池，在0.01～3V电势窗口下，以100mA/g电流密度下预锂化十圈，得到负极片。
将上述负极片与正极片以六氟磷酸锂为电解液，组装成全电池器件，在0.01～4.5V电势窗口下，以不同扫描速率测得其循环伏安曲线，在电流密度下测试其倍率性能及循环性能。
本发明所制得的富氢碳材料在锂/钠/钾离子电池及锂/钠/钾离子电容器中都具有良好的应用前景，所述富氢碳材料应用于锂离子电容器(LIC)和钠离子电容器(SIC)时，二者均具有高能量/功率密度(LIC：151.2Wh kg -1/28.4kW kg -1；SIC：100.5Wh kg -1/18.6kW kg -1)，并具有出色的倍率和循环性能。可将其作为碱金属电容器储能器件的负极材料。
所述的富氢碳材料是指含有大量氢的碳材料，为本领域专有名词，属于清楚表述。富氢 碳材料的储能机理，以储锂为例，与氢相连的sp 2杂化碳变成sp 3杂化碳进行储锂，此过程可逆，反应机理如下所示：
Figure PCTCN2021128186-appb-000001
碳源的选择会影响最终产物的含氢量，而含氢量会影响富氢碳材料的储锂/钠/钾性能；煅烧温度会影响最终产物的含氢量，而含氢量会影响富氢碳材料的储锂/钠/钾性能。
有益效果
本发明以自模板法将聚合物前驱体制备成富氢碳材料，无需掺杂，反应条件简单，使用的溶剂价格便宜，无毒无害，符合环境绿色友好的要求，有着极其广泛的应用前景。合成的富氢碳材料本身具有较大的无序度和比表面积，提供了更多的活性位点，表现出优异的可逆比容量、倍率性能和循环性能。本发明制备的富氢碳材料表现出优异的能量/功率密度和长循环寿命，有利于满足实际需求。
附图说明
图1.实施例1制备的富氢碳材料的扫描电镜图片(SEM)；
图2.实施例1制备的富氢碳材料的透射电镜图片(TEM)；
图3.实施例1制备的富氢碳材料的X射线粉末衍射图(XRD)；
图4.实施例1制备的富氢碳材料的傅立叶变换红外光谱图(FTIR)；
图5.实施例1制备的富氢碳材料的固体核磁共振谱图(MAS-ss-NMR)；
图6.实施例1、2、3制备的富氢碳材料的元素分析图(EA)；
图7.实施例1制备的富氢碳材料用于钠离子电池后的倍率和循环性能曲线；
图8.实施例1制备的富氢碳材料组装成锂离子电容器和钠离子电容器后的循环稳定性图。
具体实施方式
下面结合实施例对本发明进行详细说明，以使本领域技术人员更好地理解本发明，但本发明并不局限于以下实施例。
实施例1
一种富氢碳材料的制备方法，包括如下步骤：
A、在连续磁力搅拌下，将2g聚合前体海藻酸钠(SA)溶于100mL去离子水(DI)中，形成质量分数为2％的水溶液，标记为溶液A；
B、将1g的无水氯化铁FeCl 3溶解在100mL去离子水形成质量分数为1％的水溶 液，标记为溶液B；
C、在磁力搅拌下，将溶液A缓慢加入溶液B中，得到交联的海藻酸铁(IA)微凝胶珠，通过使用冷冻干燥机将洗涤的IA水凝胶珠粒冷冻干燥以蒸发水分；
D、将冷冻干燥的产物在Ar气氛下在水平管式炉中碳化2小时，碳化温度为600℃，将产物用1M盐酸(30％)处理以除去催化剂，得到富氢的碳纳米线(HCNW)。
样品标记为HCNW-1，其微观结构如图1和图2所示。
图3中，各衍射峰位置和相对强度均与JPCDS卡片(#38-0500)相吻合，表明产物为HCNW-1。
图4-6分别为样品的FTIR、MAS-ss-NMR、EA谱图，其结果表明HCNW样品中含有碳、氢和氧元素。
将制得的HCNW-1富氢碳材料与导电剂和粘结剂按8:1:1制作成电极，并与锂片组装成半电池，进行性能测试。其在0.1,0.25,0.5,1.0and 2.5A/g电流密度下的容量分别为1144.2,952.2,752,621.3and 471.8mAh/g；且在1.0A/g电流密度下进行了3000次循环，可达到94.2％的容量保持率，具有出色的倍率和循环性能。
将制得的HCNW-1富氢碳材料与导电剂和粘结剂按8:1:1制作成电极，并与钠片组装成半电池，进行性能测试。其在0.1,0.25,0.5,1.0and 2.5A/g电流密度下的容量分别为362.5,286.2,241.4,203.7,and 145.9mAh/g；且在1.0A/g电流密度下进行了3000次循环，可达到89.75％的容量保持率，具有出色的倍率和循环性能，如图7所示。
将制得的HCNW-1预锂/钠化后制作成锂/钠离子电容器，进行性能测试。二者均具有较高的能量密度/功率密度(锂离子电容器：151.2Wh/kg/28.4kW/kg；钠离子电容器：100.5Wh/kg/18.6kW/kg)。在1.0A/g电流密度下进行了3000次循环，锂离子电容器(LIC)具有82.16％的容量保持率，相同条件下，钠离子电容器(SIC)具有83％的容量保持率，并具有较高的库仑效率，循环过程中性能稳定性较好，如图8所示。
实施例2
一种富氢碳材料的制备方法，包括如下步骤：
A、在连续磁力搅拌下，将2g聚合前体海藻酸钠(SA)溶于100mL去离子水(DI)中，形成质量分数为2％的水溶液，标记为溶液A；
B、将1.5g的无水氯化铁FeCl 3溶解在100mL去离子水形成质量分数为1.5％的水溶液，标记为溶液B；
C、在磁力搅拌下，将溶液A缓慢加入溶液B中，得到交联的海藻酸铁(IA)微凝 胶珠，通过使用冷冻干燥机将洗涤的IA水凝胶珠粒冷冻干燥以蒸发水分；
D、将冷冻干燥的产物在Ar气氛下在水平管式炉中碳化2小时，碳化温度为700℃，将产物用1M盐酸(30％)处理以除去催化剂，得到富氢的碳纳米线(HCNW)。
样品标记为HCNW-1.5。
将本实施例制得的HCNW-1.5富氢碳材料与导电剂和粘结剂按8:1:1制作成电极，并与锂片组装成半电池，进行性能测试。在0.1A/g电流密度下的可逆容量为781.3mAh/g。
实施例3
一种富氢碳材料的制备方法，包括如下步骤：
A、在连续磁力搅拌下，将2g聚合前体海藻酸钠(SA)溶于100mL去离子水(DI)中，形成质量分数为2％的水溶液，标记为溶液A；
B、将2g的无水氯化铁FeCl 3溶解在100mL去离子水形成质量分数为2％的水溶液，标记为溶液B；
C、在磁力搅拌下，将溶液A缓慢加入溶液B中，得到交联的海藻酸铁(IA)微凝胶珠，通过使用冷冻干燥机将洗涤的IA水凝胶珠粒冷冻干燥以蒸发水分；
D、将冷冻干燥的产物在Ar气氛下在水平管式炉中碳化2小时，碳化温度为800℃，将产物用1M盐酸(30％)处理以除去催化剂，得到富氢的碳纳米线(HCNW)。
样品标记为HCNW-2。
从图6的元素分析(EA)显示，三个实施例所得HCNW样品都含有H、C、O三种元素，且三份HCNW样品的H/C原子比都约为0.5，而其O/C原子比(O含量)随Fe 3+的浓度增加而增加。
将本实施例制得的HCNW-2富氢碳材料与导电剂和粘结剂按8:1:1制作成电极，并与锂片组装成半电池，进行性能测试。在0.1A/g电流密度下的可逆容量为669.9mAh/g。
实施例4
一种富氢碳材料的制备方法，包括如下步骤：
A、在连续磁力搅拌下，将2g聚合前体羧甲基纤维素钠(CMC)溶于100mL去离子水(DI)中，形成质量分数为2％的水溶液，标记为溶液A；
B、将1g的无水氯化铁FeCl 3溶解在100mL去离子水形成质量分数为1％的水溶液，标记为溶液B；
C、在缓慢的磁力搅拌下，将溶液A缓慢加入溶液B中，得到交联的羧甲基纤维素铁微凝胶珠，通过使用冷冻干燥机将洗涤的水凝胶珠冷冻干燥以蒸发水分；
D、将冷冻干燥的产物在Ar气氛下在水平管式炉中碳化2.5小时，碳化温度为700℃，将产物用1M盐酸(30％)处理以除去催化剂，得到多孔富氢碳材料。
将本实施例制得的多孔富氢碳材料与导电剂和粘结剂按8:1:1制作成电极，并与钠片组装成半电池，进行电化学性能测试。在2.5A/g电流密度下进行了10000次循环，达到97.1％的容量保持率，具有出色的倍率和循环性能。
将本实施例制得的多孔富氢碳材料预锂/钠化后制作成钠离子电容器，进行性能测试，展现出较高的能量密度/功率密度(122Wh/kg/17.6kW/kg)。在1.0A/g电流密度下进行10000次循环后，容量保持率为95.7％，具有高的库仑效率和循环稳定性能。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (6)

  1. 一种富氢碳材料的制备方法，其特征在于，包括如下步骤：
    A.碳源溶于去离子水中配制成质量分数为2～10％的溶液,标记为溶液A，其中所述碳源为海藻酸钠、羧甲基纤维素钠或生物油；
    B.催化剂溶解在去离子水配制成质量分数为1～5％的溶液,标记为溶液B，其中所述催化剂为氯化铁、氯化锌或氯化钠；
    C.将A溶液滴加到B溶液中，搅拌下充分反应后，洗涤、冻干；
    D.干燥产物于惰性气氛中600～1000℃碳化1～5h，酸洗，即得。
  2. 根据权利要求1所述富氢碳材料的制备方法，其特征在于：步骤C中所述冻干，其温度-100～-20℃，冻干时间12～72h。
  3. 根据权利要求1所述富氢碳材料的制备方法，其特征在于：步骤D中所述惰性气体为氩气或氮气。
  4. 根据权利要求1所述富氢碳材料的制备方法，其特征在于：步骤D中所述酸洗，所用的溶液为质量分数为30％的盐酸溶液或硫酸溶液。
  5. 根据权利要求1所述富氢碳材料的制备方法，其特征在于：步骤D中所述碳化，所用设备为管式炉或箱式炉，升温速率为2～15℃·min -1。
  6. 一种根据权利要求1-5任一所述方法制备得到的富氢碳材料的应用，其特征在于：将其应用于锂/钠/钾离子电池或电容器领域。
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CN114180565A (zh) * 2021-11-19 2022-03-15 广东东岛新能源股份有限公司 一种三维多孔石墨材料及其制备方法与应用
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104891479A (zh) * 2015-05-26 2015-09-09 中国林业科学研究院林产化学工业研究所 植物基类石墨烯及其制备方法
CN106654272A (zh) * 2016-12-27 2017-05-10 陕西科技大学 一种三维多孔纳米结构碳材料的制备方法
CN107445160A (zh) * 2017-08-08 2017-12-08 中国林业科学研究院林产化学工业研究所 一种可调孔径的不可溶性海藻酸盐基超级电容活性炭及其一步炭化制备方法
CN108539197A (zh) * 2018-03-13 2018-09-14 上海交通大学 高倍率钠离子电池负极用多孔石墨化硬碳的制备方法
CN108529596A (zh) * 2018-07-20 2018-09-14 广东工业大学 一种二维薄层碳的制备方法
CN109850865A (zh) * 2019-01-29 2019-06-07 河北省科学院能源研究所 一种铁负载的海藻酸钠碳气凝胶的制备方法及其应用
CN110065934A (zh) * 2019-03-28 2019-07-30 华南农业大学 一种用于钾离子电池的纳米网络结构炭材料及其制备方法和应用
CN110451482A (zh) * 2019-08-19 2019-11-15 北京理工大学 一种氮硫共掺杂碳纳米片材料的制备方法
CN113023705A (zh) * 2021-02-05 2021-06-25 江苏大学 一种富氢碳材料的制备方法及应用于锂-钠-钾储能

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104891479A (zh) * 2015-05-26 2015-09-09 中国林业科学研究院林产化学工业研究所 植物基类石墨烯及其制备方法
CN106654272A (zh) * 2016-12-27 2017-05-10 陕西科技大学 一种三维多孔纳米结构碳材料的制备方法
CN107445160A (zh) * 2017-08-08 2017-12-08 中国林业科学研究院林产化学工业研究所 一种可调孔径的不可溶性海藻酸盐基超级电容活性炭及其一步炭化制备方法
CN108539197A (zh) * 2018-03-13 2018-09-14 上海交通大学 高倍率钠离子电池负极用多孔石墨化硬碳的制备方法
CN108529596A (zh) * 2018-07-20 2018-09-14 广东工业大学 一种二维薄层碳的制备方法
CN109850865A (zh) * 2019-01-29 2019-06-07 河北省科学院能源研究所 一种铁负载的海藻酸钠碳气凝胶的制备方法及其应用
CN110065934A (zh) * 2019-03-28 2019-07-30 华南农业大学 一种用于钾离子电池的纳米网络结构炭材料及其制备方法和应用
CN110451482A (zh) * 2019-08-19 2019-11-15 北京理工大学 一种氮硫共掺杂碳纳米片材料的制备方法
CN113023705A (zh) * 2021-02-05 2021-06-25 江苏大学 一种富氢碳材料的制备方法及应用于锂-钠-钾储能

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