CN106784771A - A kind of preparation method and system of zinc antimony alloy composite negative pole material - Google Patents
A kind of preparation method and system of zinc antimony alloy composite negative pole material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 229910001245 Sb alloy Inorganic materials 0.000 title claims abstract description 28
- 239000002140 antimony alloy Substances 0.000 title claims abstract description 28
- CZJCMXPZSYNVLP-UHFFFAOYSA-N antimony zinc Chemical compound [Zn].[Sb] CZJCMXPZSYNVLP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title description 3
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 34
- 239000007773 negative electrode material Substances 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000005087 graphitization Methods 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 28
- 238000012546 transfer Methods 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052787 antimony Inorganic materials 0.000 claims description 14
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- -1 Polypropylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
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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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- 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
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Abstract
本发明公开了一种锌锑合金复合负极材料的制备方法及系统，该系统包括碳材料制备装置和复合材料制备装置两部分，碳材料制备装置包括依次连接的搅拌釜、碳化炉和石墨化炉，复合材料制备装置包括依次连接的混料机、高能球磨机和放电等离子烧结机，其中，石墨化炉与混料机连接。本发明将锌锑合金与特殊处理后的碳材料复合在一起，制备得到的复合负极材料具有极佳的循环稳定性，电学性能佳。本发明的制备系统包括依次连接的碳材料制备装置和复合材料制备装置两部分，连续生产，大大提高了生产效率。
The invention discloses a method and system for preparing a zinc-antimony alloy composite negative electrode material. The system includes two parts: a carbon material preparation device and a composite material preparation device. The carbon material preparation device includes a stirring tank, a carbonization furnace and a graphitization furnace connected in sequence , The composite material preparation device includes a mixer, a high-energy ball mill and a spark plasma sintering machine connected in sequence, wherein the graphitization furnace is connected with the mixer. The invention combines the zinc-antimony alloy with the carbon material after special treatment, and the prepared composite negative electrode material has excellent cycle stability and good electrical performance. The preparation system of the present invention includes two parts, a carbon material preparation device and a composite material preparation device connected in sequence, for continuous production, which greatly improves production efficiency.
Description
技术领域technical field
本发明涉及一种合金材料，具体涉及一种锌锑合金复合负极材料的制备方法及系统。属于有色金属材料加工技术领域。The invention relates to an alloy material, in particular to a preparation method and system for a zinc-antimony alloy composite negative electrode material. It belongs to the technical field of non-ferrous metal material processing.
背景技术Background technique
能源是人类社会发展的重要物质基础，但是，随着煤炭、石油和天然气等矿物能源的存量锐减，人类社会面临的资源枯竭压力越来越大，因此，如何提高能源使用率和开发利用可再生能源已经成为各国政府和科研人员的共同目标。Energy is an important material basis for the development of human society. However, with the sharp decline in the stock of mineral energy such as coal, oil and natural gas, human society is facing increasing pressure on resource depletion. Therefore, how to improve energy utilization and develop and utilize available resources Renewable energy has become a common goal of governments and researchers in various countries.
电池是一种化学能和电能的存储和转化装置。其中，锂离子电池因其具有电压高、比能量高、充放电寿命长、无记忆效应、无污染、工作温度范围宽、快速充电、自放电率低和安全可靠等优点，已经成为现代通讯和便携式电子产品等的理想化学电源。A battery is a storage and conversion device for chemical and electrical energy. Among them, lithium-ion batteries have become a modern communication and Ideal chemical power supply for portable electronics and more.
目前商业化的锂离子电池普遍采用石墨材料作为负极，它的理论比容量仅为372mAh/g，且在快速充放电过程中存在石墨层剥落现象，导致明显的容量衰减。而且，在快速充放电过程中容易产生锂枝晶现象，这些因素都严重制约了在动力锂离子电池中的应用。因此，采用其他材料代替石墨负极是目前锂离子电池的研究重点和难点所在。At present, commercial lithium-ion batteries generally use graphite material as the negative electrode. Its theoretical specific capacity is only 372mAh/g, and the graphite layer peels off during the rapid charge and discharge process, resulting in significant capacity attenuation. Moreover, lithium dendrites are prone to occur during rapid charging and discharging, and these factors seriously restrict the application in power lithium-ion batteries. Therefore, the use of other materials to replace the graphite anode is the current research focus and difficulty of lithium-ion batteries.
发明内容Contents of the invention
本发明的目的是为克服上述现有技术的不足，提供一种锌锑合金复合负极材料的制备方法。The object of the present invention is to provide a method for preparing a zinc-antimony alloy composite negative electrode material in order to overcome the above-mentioned deficiencies in the prior art.
本发明还提供了上述制备方法对应的一种锌锑合金复合负极材料的制备系统。The present invention also provides a preparation system of a zinc-antimony alloy composite negative electrode material corresponding to the above preparation method.
为实现上述目的，本发明采用下述技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种锌锑合金复合负极材料的制备方法，具体步骤如下：A preparation method of a zinc-antimony alloy composite negative electrode material, the specific steps are as follows:
(1)将石墨粉和环氧树脂粉按照质量比1：0.5～0.8加入搅拌釜中，以20～25℃/min的速率升温至450～550℃，搅拌4～5小时；转移至碳化炉中，氮气保护下，1600～1700℃保温2～3小时，转移至石墨化炉中，升温至2500～2600℃保温12～15小时，得到碳材料；(1) Add graphite powder and epoxy resin powder into the stirring tank according to the mass ratio of 1:0.5~0.8, raise the temperature to 450~550°C at a rate of 20~25°C/min, stir for 4~5 hours; transfer to the carbonization furnace , under the protection of nitrogen, keep warm at 1600-1700°C for 2-3 hours, transfer to a graphitization furnace, raise the temperature to 2500-2600°C and keep warm for 12-15 hours to obtain carbon materials;
(2)将步骤(1)所得碳材料与锌粉、锑粉按照摩尔比1：2～3：3～4于混料机中混合均匀，转移至高能球磨机，研磨10～20小时，转移至放电等离子烧结机，在30～1000MPa和200～600℃条件下烧结5～8分钟，即得锌锑合金复合负极材料。(2) Mix the carbon material obtained in step (1) with zinc powder and antimony powder in a mixer in a molar ratio of 1:2 to 3:3 to 4, transfer to a high energy ball mill, grind for 10 to 20 hours, and transfer to Spark plasma sintering machine, sintering at 30-1000MPa and 200-600°C for 5-8 minutes to obtain zinc-antimony alloy composite negative electrode material.
优选的，步骤(1)中，石墨粉的平均粒径为10～15μm，环氧树脂粉的平均粒径≤5μm。Preferably, in step (1), the average particle diameter of the graphite powder is 10-15 μm, and the average particle diameter of the epoxy resin powder is ≤5 μm.
优选的，步骤(2)中，碳材料、锌粉和锑粉混合均匀后，使用23w.t.％的氢氧化钠溶液进行充分洗涤。Preferably, in step (2), after the carbon material, zinc powder and antimony powder are uniformly mixed, they are fully washed with 23w.t.% sodium hydroxide solution.
优选的，步骤(2)中研磨时充入氮气保护。Preferably, nitrogen protection is charged during grinding in step (2).
上述制备方法对应的一种锌锑合金复合负极材料的制备系统，包括碳材料制备装置和复合材料制备装置两部分，所述碳材料制备装置包括依次连接的搅拌釜、碳化炉和石墨化炉，所述复合材料制备装置包括依次连接的混料机、高能球磨机和放电等离子烧结机，其中，石墨化炉与混料机连接。A zinc-antimony alloy composite negative electrode material preparation system corresponding to the above preparation method includes two parts: a carbon material preparation device and a composite material preparation device. The carbon material preparation device includes a stirring tank, a carbonization furnace and a graphitization furnace connected in sequence, The composite material preparation device includes a mixer, a high-energy ball mill and a spark plasma sintering machine connected in sequence, wherein the graphitization furnace is connected with the mixer.
优选的，所述混料机与高能球磨机之间还设有碱洗池。Preferably, an alkali washing tank is also provided between the mixer and the high-energy ball mill.
进一步优选，所述碱洗池的上方设有若干个喷淋头，喷淋头与氢氧化钠溶液储罐连接。Further preferably, several spray heads are arranged above the alkaline washing pool, and the spray heads are connected with the sodium hydroxide solution storage tank.
本发明的有益效果：Beneficial effects of the present invention:
本发明将锌锑合金与特殊处理后的碳材料复合在一起，制备得到的复合负极材料具有极佳的循环稳定性，电学性能佳。本发明的制备系统包括依次连接的碳材料制备装置和复合材料制备装置两部分，连续生产，大大提高了生产效率。The invention combines the zinc-antimony alloy with the carbon material after special treatment, and the prepared composite negative electrode material has excellent cycle stability and good electrical performance. The preparation system of the present invention includes two parts, a carbon material preparation device and a composite material preparation device connected in sequence, for continuous production, which greatly improves production efficiency.
附图说明Description of drawings
图1是本发明的制备系统结构示意图；Fig. 1 is a schematic structural diagram of the preparation system of the present invention;
其中，1为碳材料制备装置，2为复合材料制备装置，11为搅拌釜，12为碳化炉，13为石墨化炉，21为混料机，22为碱洗池，23为高能球磨机，24为放电等离子烧结机。Among them, 1 is a carbon material preparation device, 2 is a composite material preparation device, 11 is a stirring tank, 12 is a carbonization furnace, 13 is a graphitization furnace, 21 is a mixer, 22 is an alkali cleaning tank, 23 is a high-energy ball mill, 24 It is spark plasma sintering machine.
具体实施方式detailed description
下面结合附图和实施例对本发明进行进一步的阐述，应该说明的是，下述说明仅是为了解释本发明，并不对其内容进行限定。The present invention will be further described below in conjunction with the accompanying drawings and embodiments. It should be noted that the following description is only for explaining the present invention and not limiting its content.
实施例1：Example 1:
一种锌锑合金复合负极材料的制备方法，具体步骤如下：A preparation method of a zinc-antimony alloy composite negative electrode material, the specific steps are as follows:
(1)将石墨粉和环氧树脂粉按照质量比1：0.5加入搅拌釜11中，以20℃/min的速率升温至450℃，搅拌4小时；转移至碳化炉12中，氮气保护下，1600℃保温2小时，转移至石墨化炉13中，升温至2500℃保温12小时，得到碳材料；(1) Add graphite powder and epoxy resin powder into the stirring tank 11 according to the mass ratio of 1:0.5, raise the temperature to 450°C at a rate of 20°C/min, and stir for 4 hours; transfer to the carbonization furnace 12, under the protection of nitrogen, heat preservation at 1600°C for 2 hours, transfer to graphitization furnace 13, heat up to 2500°C and heat preservation for 12 hours to obtain carbon material;
(2)将步骤(1)所得碳材料与锌粉、锑粉按照摩尔比1：2：3于混料机21中混合均匀，转移至高能球磨机23，研磨10小时(充入氮气保护)，转移至放电等离子烧结机24，在30MPa和200℃条件下烧结5分钟，即得锌锑合金复合负极材料。(2) Mix the carbon material obtained in step (1) with zinc powder and antimony powder in the mixer 21 according to the molar ratio of 1:2:3, transfer to the high-energy ball mill 23, and grind for 10 hours (filled with nitrogen protection), Transfer to spark plasma sintering machine 24, and sinter at 30 MPa and 200° C. for 5 minutes to obtain zinc-antimony alloy composite negative electrode material.
步骤(1)中，石墨粉的平均粒径为10μm，环氧树脂粉的平均粒径≤5μm。In step (1), the average particle diameter of the graphite powder is 10 μm, and the average particle diameter of the epoxy resin powder is ≤5 μm.
步骤(2)中，碳材料、锌粉和锑粉混合均匀后，使用23w.t.％的氢氧化钠溶液进行充分洗涤。In step (2), after the carbon material, zinc powder and antimony powder are uniformly mixed, they are fully washed with 23w.t.% sodium hydroxide solution.
如图1所示，一种锌锑合金复合负极材料的制备系统，包括碳材料制备装置1和复合材料制备装置2两部分，碳材料制备装置1包括依次连接的搅拌釜11、碳化炉12和石墨化炉13，复合材料制备装置2包括依次连接的混料机21、高能球磨机23和放电等离子烧结机24，其中，石墨化炉13与混料机21连接。As shown in Fig. 1, a kind of preparation system of zinc-antimony alloy composite negative electrode material comprises two parts of carbon material preparation device 1 and composite material preparation device 2, and carbon material preparation device 1 comprises a stirring tank 11, carbonization furnace 12 and The graphitization furnace 13 and the composite material preparation device 2 include a mixer 21 , a high-energy ball mill 23 and a spark plasma sintering machine 24 connected in sequence, wherein the graphitization furnace 13 is connected to the mixer 21 .
混料机21与高能球磨机23之间还设有碱洗池22。碱洗池22的上方设有若干个喷淋头，喷淋头与氢氧化钠溶液储罐连接。An alkali washing tank 22 is also provided between the mixer 21 and the high-energy ball mill 23 . The top of the alkali washing tank 22 is provided with several shower heads, and the shower heads are connected with the sodium hydroxide solution storage tank.
实施例2：Example 2:
一种锌锑合金复合负极材料的制备方法，具体步骤如下：A preparation method of a zinc-antimony alloy composite negative electrode material, the specific steps are as follows:
(1)将石墨粉和环氧树脂粉按照质量比1：0.8加入搅拌釜11中，以25℃/min的速率升温至550℃，搅拌5小时；转移至碳化炉12中，氮气保护下，1700℃保温3小时，转移至石墨化炉13中，升温至2600℃保温15小时，得到碳材料；(1) Add graphite powder and epoxy resin powder into the stirring tank 11 according to the mass ratio of 1:0.8, raise the temperature to 550°C at a rate of 25°C/min, and stir for 5 hours; transfer to the carbonization furnace 12, under the protection of nitrogen, heat preservation at 1700°C for 3 hours, transfer to graphitization furnace 13, heat up to 2600°C and heat preservation for 15 hours to obtain carbon material;
(2)将步骤(1)所得碳材料与锌粉、锑粉按照摩尔比1：3：4于混料机21中混合均匀，转移至高能球磨机23，研磨20小时(充入氮气保护)，转移至放电等离子烧结机24，在1000MPa和600℃条件下烧结8分钟，即得锌锑合金复合负极材料。(2) Mix the carbon material obtained in step (1) with zinc powder and antimony powder in the mixer 21 according to the molar ratio of 1:3:4, transfer to the high-energy ball mill 23, and grind for 20 hours (filled with nitrogen protection), Transfer to spark plasma sintering machine 24, and sinter at 1000 MPa and 600° C. for 8 minutes to obtain zinc-antimony alloy composite negative electrode material.
步骤(1)中，石墨粉的平均粒径为15μm，环氧树脂粉的平均粒径≤5μm。In step (1), the average particle diameter of the graphite powder is 15 μm, and the average particle diameter of the epoxy resin powder is ≤5 μm.
步骤(2)中，碳材料、锌粉和锑粉混合均匀后，使用23w.t.％的氢氧化钠溶液进行充分洗涤。In step (2), after the carbon material, zinc powder and antimony powder are uniformly mixed, they are fully washed with 23w.t.% sodium hydroxide solution.
一种锌锑合金复合负极材料的制备系统，同实施例1。A preparation system for a zinc-antimony alloy composite negative electrode material, the same as in Example 1.
实施例3：Example 3:
一种锌锑合金复合负极材料的制备方法，具体步骤如下：A preparation method of a zinc-antimony alloy composite negative electrode material, the specific steps are as follows:
(1)将石墨粉和环氧树脂粉按照质量比1：0.5加入搅拌釜11中，以25℃/min的速率升温至450℃，搅拌5小时；转移至碳化炉12中，氮气保护下，1600℃保温3小时，转移至石墨化炉13中，升温至2500℃保温15小时，得到碳材料；(1) Add graphite powder and epoxy resin powder into the stirring tank 11 according to the mass ratio of 1:0.5, heat up to 450°C at a rate of 25°C/min, and stir for 5 hours; transfer to the carbonization furnace 12, under nitrogen protection, heat preservation at 1600°C for 3 hours, transfer to graphitization furnace 13, heat up to 2500°C and heat preservation for 15 hours to obtain carbon material;
(2)将步骤(1)所得碳材料与锌粉、锑粉按照摩尔比1：2：4于混料机21中混合均匀，转移至高能球磨机23，研磨10小时(充入氮气保护)，转移至放电等离子烧结机24，在1000MPa和200℃条件下烧结8分钟，即得锌锑合金复合负极材料。(2) Mix the carbon material obtained in step (1) with zinc powder and antimony powder in the mixer 21 according to the molar ratio of 1:2:4, transfer to the high-energy ball mill 23, and grind for 10 hours (filled with nitrogen protection), Transfer to spark plasma sintering machine 24, and sinter at 1000 MPa and 200° C. for 8 minutes to obtain zinc-antimony alloy composite negative electrode material.
步骤(1)中，石墨粉的平均粒径为10μm，环氧树脂粉的平均粒径≤5μm。In step (1), the average particle diameter of the graphite powder is 10 μm, and the average particle diameter of the epoxy resin powder is ≤5 μm.
步骤(2)中，碳材料、锌粉和锑粉混合均匀后，使用23w.t.％的氢氧化钠溶液进行充分洗涤。In step (2), after the carbon material, zinc powder and antimony powder are uniformly mixed, they are fully washed with 23w.t.% sodium hydroxide solution.
一种锌锑合金复合负极材料的制备系统，同实施例1。A preparation system for a zinc-antimony alloy composite negative electrode material, the same as in Example 1.
实施例4：Example 4:
一种锌锑合金复合负极材料的制备方法，具体步骤如下：A preparation method of a zinc-antimony alloy composite negative electrode material, the specific steps are as follows:
(1)将石墨粉和环氧树脂粉按照质量比1：0.8加入搅拌釜11中，以20℃/min的速率升温至550℃，搅拌4小时；转移至碳化炉12中，氮气保护下，1700℃保温2小时，转移至石墨化炉13中，升温至2600℃保温12小时，得到碳材料；(1) Add graphite powder and epoxy resin powder into the stirring tank 11 according to the mass ratio of 1:0.8, heat up to 550°C at a rate of 20°C/min, and stir for 4 hours; transfer to the carbonization furnace 12, under nitrogen protection, heat preservation at 1700°C for 2 hours, transfer to graphitization furnace 13, heat up to 2600°C and heat preservation for 12 hours to obtain carbon material;
(2)将步骤(1)所得碳材料与锌粉、锑粉按照摩尔比1：3：3于混料机21中混合均匀，转移至高能球磨机23，研磨20小时(充入氮气保护)，转移至放电等离子烧结机24，在30MPa和600℃条件下烧结5分钟，即得锌锑合金复合负极材料。(2) Mix the carbon material obtained in step (1) with zinc powder and antimony powder in the mixer 21 according to the molar ratio of 1:3:3, transfer to the high-energy ball mill 23, and grind for 20 hours (filled with nitrogen protection), Transfer to spark plasma sintering machine 24, and sinter at 30 MPa and 600° C. for 5 minutes to obtain zinc-antimony alloy composite negative electrode material.
步骤(1)中，石墨粉的平均粒径为15μm，环氧树脂粉的平均粒径≤5μm。In step (1), the average particle diameter of the graphite powder is 15 μm, and the average particle diameter of the epoxy resin powder is ≤5 μm.
步骤(2)中，碳材料、锌粉和锑粉混合均匀后，使用23w.t.％的氢氧化钠溶液进行充分洗涤。In step (2), after the carbon material, zinc powder and antimony powder are uniformly mixed, they are fully washed with 23w.t.% sodium hydroxide solution.
一种锌锑合金复合负极材料的制备系统，同实施例1。A preparation system for a zinc-antimony alloy composite negative electrode material, the same as in Example 1.
实施例5：Example 5:
一种锌锑合金复合负极材料的制备方法，具体步骤如下：A preparation method of a zinc-antimony alloy composite negative electrode material, the specific steps are as follows:
(1)将石墨粉和环氧树脂粉按照质量比1：0.7加入搅拌釜11中，以22℃/min的速率升温至500℃，搅拌4.5小时；转移至碳化炉12中，氮气保护下，1650℃保温2.5小时，转移至石墨化炉13中，升温至2550℃保温13小时，得到碳材料；(1) Add graphite powder and epoxy resin powder into the stirring tank 11 according to the mass ratio of 1:0.7, raise the temperature to 500°C at a rate of 22°C/min, and stir for 4.5 hours; transfer to the carbonization furnace 12, under the protection of nitrogen, heat preservation at 1650°C for 2.5 hours, transfer to the graphitization furnace 13, heat up to 2550°C and heat preservation for 13 hours to obtain carbon material;
(2)将步骤(1)所得碳材料与锌粉、锑粉按照摩尔比1：2.5：3.5于混料机21中混合均匀，转移至高能球磨机23，研磨15小时(充入氮气保护)，转移至放电等离子烧结机24，在500MPa和400℃条件下烧结7分钟，即得锌锑合金复合负极材料。(2) Mix the carbon material obtained in step (1) with zinc powder and antimony powder in the mixer 21 according to the molar ratio of 1:2.5:3.5, transfer to the high-energy ball mill 23, and grind for 15 hours (filled with nitrogen protection), Transfer to spark plasma sintering machine 24, and sinter at 500 MPa and 400° C. for 7 minutes to obtain zinc-antimony alloy composite negative electrode material.
步骤(1)中，石墨粉的平均粒径为12μm，环氧树脂粉的平均粒径≤5μm。In step (1), the average particle diameter of the graphite powder is 12 μm, and the average particle diameter of the epoxy resin powder is ≤5 μm.
步骤(2)中，碳材料、锌粉和锑粉混合均匀后，使用23w.t.％的氢氧化钠溶液进行充分洗涤。In step (2), after the carbon material, zinc powder and antimony powder are uniformly mixed, they are fully washed with 23w.t.% sodium hydroxide solution.
一种锌锑合金复合负极材料的制备系统，同实施例1。A preparation system for a zinc-antimony alloy composite negative electrode material, the same as in Example 1.
试验例Test case
将实施例1～5所得的复合负极材料均匀涂覆于铜箔上制成电极，采用金属钠片为正极，电解液为1mol/L的NaClO4/EC-DMC(体积比为1：1)，聚丙烯微孔薄膜(Celgard 2300)为隔膜，组装成钠离子半电池，测试循环稳定性，即在0.1C倍率下，0.01～1.8V电压范围内的长时间循环50次循环后比容量，结果见表1。The composite negative electrode material obtained in Examples 1-5 is evenly coated on the copper foil to make an electrode, the metal sodium sheet is used as the positive electrode, and the electrolyte is 1mol/L NaClO 4 /EC-DMC (volume ratio is 1:1) , Polypropylene microporous film (Celgard 2300) is used as a separator, assembled into a sodium ion half-cell, and the cycle stability is tested, that is, the specific capacity after 50 cycles of long-term cycling in the voltage range of 0.01-1.8V at a rate of 0.1C, The results are shown in Table 1.
表1.循环稳定性测试结果Table 1. Cycle Stability Test Results
由表1可得出结论，本发明的复合负极材料具有极佳的循环稳定性。It can be concluded from Table 1 that the composite negative electrode material of the present invention has excellent cycle stability.
上述虽然结合附图对本发明的具体实施方式进行了描述，但并非对本发明保护范围的限制，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。Although the specific implementation of the present invention has been described above in conjunction with the accompanying drawings, it does not limit the protection scope of the present invention. On the basis of the technical solution of the present invention, those skilled in the art can make various Modifications or variations are still within the protection scope of the present invention.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112768646A (en) * | 2020-12-04 | 2021-05-07 | 杭州电子科技大学 | Method for preparing antimony-based alloy/nitrogen-doped carbon composite porous material by self-template method, composite porous material and application |
| CN115986099A (en) * | 2022-12-15 | 2023-04-18 | 天津大学 | Three-dimensional carbon skeleton zinc composite material for dendrite-free zinc metal battery cathode and preparation method thereof |
| CN116014093A (en) * | 2022-12-15 | 2023-04-25 | 天津大学 | High-conductivity functional group heterogeneous-phase connection material at zinc grain boundary and preparation method thereof |
| CN118352456A (en) * | 2024-05-17 | 2024-07-16 | 广东工业大学 | A temperature compensating alloy negative electrode and zinc battery application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005347076A (en) * | 2004-06-02 | 2005-12-15 | Pionics Co Ltd | Negative electrode active material particle for lithium secondary battery and manufacturing method of negative electrode |
| US20100159328A1 (en) * | 2008-12-23 | 2010-06-24 | Snu R&Db Foundation | Preparation method of znsb-c composite and anode materials for secondary batteries containing the same composite |
| CN101847721A (en) * | 2010-05-19 | 2010-09-29 | 宁波职业技术学院 | Carbon-coated antimony-zinc alloy material of cathode for lithium-ion battery and method for preparing same |
| CN103050673A (en) * | 2012-12-26 | 2013-04-17 | 上海锦众信息科技有限公司 | Preparation method of carbon coated antimony composite materials for lithium ion batteries |
| CN103199254A (en) * | 2013-04-03 | 2013-07-10 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite negative material of lithium-ion battery and preparation method of negative material |
| CN103219495A (en) * | 2013-04-08 | 2013-07-24 | 廖小玉 | Preparation method of zinc antimony alloy-carbon composite negative electrode material |
| KR20150052476A (en) * | 2013-11-06 | 2015-05-14 | 금오공과대학교 산학협력단 | Method for manufacturing binary metal compound composite, rechargeable battery comprising the same |
| CN206639862U (en) * | 2017-03-24 | 2017-11-14 | 南昌专腾科技有限公司 | A kind of preparation system of zinc antimony alloy composite negative pole material |
-
2017
- 2017-03-24 CN CN201710182921.8A patent/CN106784771A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005347076A (en) * | 2004-06-02 | 2005-12-15 | Pionics Co Ltd | Negative electrode active material particle for lithium secondary battery and manufacturing method of negative electrode |
| US20100159328A1 (en) * | 2008-12-23 | 2010-06-24 | Snu R&Db Foundation | Preparation method of znsb-c composite and anode materials for secondary batteries containing the same composite |
| CN101847721A (en) * | 2010-05-19 | 2010-09-29 | 宁波职业技术学院 | Carbon-coated antimony-zinc alloy material of cathode for lithium-ion battery and method for preparing same |
| CN103050673A (en) * | 2012-12-26 | 2013-04-17 | 上海锦众信息科技有限公司 | Preparation method of carbon coated antimony composite materials for lithium ion batteries |
| CN103199254A (en) * | 2013-04-03 | 2013-07-10 | 深圳市贝特瑞新能源材料股份有限公司 | Graphite negative material of lithium-ion battery and preparation method of negative material |
| CN103219495A (en) * | 2013-04-08 | 2013-07-24 | 廖小玉 | Preparation method of zinc antimony alloy-carbon composite negative electrode material |
| KR20150052476A (en) * | 2013-11-06 | 2015-05-14 | 금오공과대학교 산학협력단 | Method for manufacturing binary metal compound composite, rechargeable battery comprising the same |
| CN206639862U (en) * | 2017-03-24 | 2017-11-14 | 南昌专腾科技有限公司 | A kind of preparation system of zinc antimony alloy composite negative pole material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112768646A (en) * | 2020-12-04 | 2021-05-07 | 杭州电子科技大学 | Method for preparing antimony-based alloy/nitrogen-doped carbon composite porous material by self-template method, composite porous material and application |
| CN115986099A (en) * | 2022-12-15 | 2023-04-18 | 天津大学 | Three-dimensional carbon skeleton zinc composite material for dendrite-free zinc metal battery cathode and preparation method thereof |
| CN116014093A (en) * | 2022-12-15 | 2023-04-25 | 天津大学 | High-conductivity functional group heterogeneous-phase connection material at zinc grain boundary and preparation method thereof |
| CN115986099B (en) * | 2022-12-15 | 2024-05-14 | 天津大学 | A three-dimensional carbon skeleton zinc composite material for dendrite-free zinc metal battery negative electrode and preparation method thereof |
| CN116014093B (en) * | 2022-12-15 | 2024-11-08 | 天津大学 | High-conductivity functional group heterogeneous-phase connection material at zinc grain boundary and preparation method thereof |
| CN118352456A (en) * | 2024-05-17 | 2024-07-16 | 广东工业大学 | A temperature compensating alloy negative electrode and zinc battery application |
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