CN1505188A - Composite nano metal negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Composite nano metal negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN1505188A CN1505188A CNA021546541A CN02154654A CN1505188A CN 1505188 A CN1505188 A CN 1505188A CN A021546541 A CNA021546541 A CN A021546541A CN 02154654 A CN02154654 A CN 02154654A CN 1505188 A CN1505188 A CN 1505188A
- Authority
- CN
- China
- Prior art keywords
- negative electrode
- metal
- electrode material
- lithium
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002131 composite material Substances 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 229920000620 organic polymer Polymers 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 239000002952 polymeric resin Substances 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920006037 cross link polymer Polymers 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 239000011149 active material Substances 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000011440 grout Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910013458 LiC6 Inorganic materials 0.000 description 1
- 229910008433 SnCU Inorganic materials 0.000 description 1
- 229910008452 SnFe Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- -1 etc. Polymers 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明涉及一种锂离子电池用复合纳米金属负极材料及其制备方法，其特征为：材料表观为固体粉末，粒径为2～25μm；其结构为纳米金属或合金颗粒分散分布在具有介孔结构的无定型碳中；材料含碳量0.5～50％，锡基金属含量50～99.5％；其制备方法是金属氧化物分散于有机聚合物树脂中、有机聚合物树脂碳化和金属氧化物的热还原：解决了金属或合金作为负极材料的在循环过程中的粉化问题；解决了纳米活性材料的循环过程中的聚集问题；改善了金属或合金作为负极材料的电化学循环性能，使其实用于电池的生产。The invention relates to a composite nano-metal negative electrode material for lithium-ion batteries and a preparation method thereof. In amorphous carbon with pore structure; the carbon content of the material is 0.5-50%, and the tin-based metal content is 50-99.5%; the preparation method is that the metal oxide is dispersed in the organic polymer resin, the organic polymer resin is carbonized and the metal oxide Thermal reduction: solve the problem of pulverization of metal or alloy as negative electrode material in the cycle process; solve the aggregation problem of nano active material in the cycle process; improve the electrochemical cycle performance of metal or alloy as negative electrode material, so that It is actually used in the production of batteries.
Description
技术领域：Technical field:
本发明涉及一种锂离子电池用复合纳米金属负极材料及其制备方法。The invention relates to a composite nano metal negative electrode material for a lithium ion battery and a preparation method thereof.
背景技术：Background technique:
锂离子电池作为新一代化学电源，其性能特点主要取决于其制作材料的性能：其中负极活性材料是其关键材料之一。目前商品化的锂离子电池主要用碳系(人工碳、人工石墨、处理天然石墨等)负极活性材料(J.R.Dahn，etal[J]，Science，1995，270：590-593)，但其可逆储锂容量较低；与碳系材料相比，金属及合金类负极材料则具有较高的储锂容量，因而引起研究者注意(李泓，等，电化学，6(2)，131(2000))。如已有研究的Si、Ge、Sn、Pb、Al、Ga、Sb、In、Cd、Zn等，其中金属锡的理论比容量为990mAh/g，硅为4200mAh/g，远高于石墨插入化合物LiC6的理论容量372mAh/g。但锂反复的嵌入脱出导致合金类电极在充放电过程中体积变化较大，逐渐粉化失效，因而循环性较差。As a new generation of chemical power source, the performance characteristics of lithium-ion batteries mainly depend on the properties of their materials: among them, the negative electrode active material is one of its key materials. Currently commercialized lithium-ion batteries mainly use carbon-based (artificial carbon, artificial graphite, processed natural graphite, etc.) Lithium capacity is low; Compared with carbon-based materials, metal and alloy anode materials have higher lithium storage capacity, thus attracting the attention of researchers (Li Hong, et al., Electrochemistry, 6(2), 131(2000) ). For example, Si, Ge, Sn, Pb, Al, Ga, Sb, In, Cd, Zn, etc. have been studied, among which the theoretical specific capacity of metal tin is 990mAh/g, and silicon is 4200mAh/g, which is much higher than that of graphite intercalation compounds. The theoretical capacity of LiC6 is 372mAh/g. However, the repeated intercalation and deintercalation of lithium leads to a large volume change of the alloy electrode during charging and discharging, and gradually pulverizes and fails, so the cycle performance is poor.
目前正在研究的解决循环性能差的一种办法是采用超细合金及活性/非活性合金分散体系。超细合金每个颗粒在充放电过程中的绝对体积变化较小，非活性材料起到分散、缓冲介质的作用；理论上应具有好的循环性和较小的容量损失。已经报导的包括SnS-bx、SnAgx、SnFe、SnCu、C/Si、nano-Si等。但至今仍未解决合金在电化学循环过程中聚集而容量下降、循环性能差的问题。One way to solve the poor cycle performance that is currently being studied is to use ultra-fine alloys and active/inactive alloy dispersion systems. The absolute volume change of each particle of the ultrafine alloy is small during the charge and discharge process, and the inactive material plays the role of dispersion and buffer medium; in theory, it should have good circulation and small capacity loss. Those that have been reported include SnS-bx, SnAgx, SnFe, SnCu, C/Si, nano-Si, etc. However, the problem of the aggregation of the alloy during the electrochemical cycle and the decrease in capacity and poor cycle performance has not been solved so far.
发明内容：Invention content:
本发明的目的是克服现有技术的不足之处，尤其是电化学循环性能差的问题，为生产具有能量密度大、循环寿命长、自放电小、无记忆效应等优良性能的锂离子电池而提供金属负极材料。The purpose of the present invention is to overcome the deficiencies of the prior art, especially the problem of poor electrochemical cycle performance, for the production of lithium ion batteries with high energy density, long cycle life, small self-discharge, and no memory effect. Provide metal anode materials.
本发明所指的锂离子电池用金属系负极材料主要是金属锡或锡基合金或锑、铅、铟、镉、锌、铜、铁等易于由氧化物高温碳还原制取的金属及合金；这些材料表观为固体粉末，粒径为2～25μm；其结构为纳米金属或合金颗粒分散分布在具有介孔结构的无定型碳中；材料含碳量0.5～50％，金属或合金含量50～99.5％。Metal-based negative electrode materials for lithium-ion batteries referred to in the present invention are mainly metals and alloys that are easily produced by high-temperature carbon reduction of oxides such as metal tin or tin-based alloys or antimony, lead, indium, cadmium, zinc, copper, and iron; These materials appear as solid powder with a particle size of 2 to 25 μm; their structure is that nanometer metal or alloy particles are dispersed in amorphous carbon with a mesoporous structure; the carbon content of the material is 0.5 to 50%, and the metal or alloy content is 50% ~99.5%.
本发明所指的锂离子电池用金属负极材料的制备方法是以纳米金属氧化物和有机聚合物树脂为材料；金属氧化物分散于有机聚合物树脂中、有机聚合物树脂碳化和金属氧化物的热还原等步骤。其特征为：The preparation method of the lithium ion battery metal negative electrode material that the present invention refers is to take nanometer metal oxide and organic polymer resin as material; Metal oxide is dispersed in the organic polymer resin, organic polymer resin carbonization and metal oxide Steps such as thermal reduction. Its characteristics are:
①采用超声波分散法，将粒径20～200nm的金属氧化物粉末分散在有机聚合物树脂的酒精溶液中；并于80～100℃下干燥。①Use the ultrasonic dispersion method to disperse the metal oxide powder with a particle size of 20-200nm in the alcohol solution of the organic polymer resin; and dry it at 80-100°C.
②将上述干燥物置于一可通气的炉子中，在氮气或氩气保护气氛或真空和400～1500℃下进行有机聚合物的裂解和金属化物的热还原；高温热处理的停留时间为0.1～24小时。②Put the above-mentioned dry matter in a ventilated furnace, and carry out cracking of organic polymers and thermal reduction of metallized compounds in nitrogen or argon protective atmosphere or vacuum at 400-1500°C; the residence time of high-temperature heat treatment is 0.1-24 Hour.
上述方法中，采用的有机聚合物树脂可以是线性高分子，如聚苯乙烯、线性酚醛树脂等，也可以是交联高分子树脂，如交联的聚苯乙烯、交联酚醛树脂等。In the above method, the organic polymer resin used can be a linear polymer, such as polystyrene, novolac resin, etc., or a crosslinked polymer resin, such as crosslinked polystyrene, crosslinked phenolic resin, etc.
上述方法中所述的热处理方法包括两种方法：The heat treatment method described in the above method includes two methods:
①一步热处理法：直接在一定温度下使有机聚合物裂解的金属氧化物热还原同时发生，一步形成本发明所指的材料；1. one-step heat treatment method: directly at a certain temperature, the metal oxide thermal reduction of the organic polymer cracking occurs simultaneously, and the material referred to in the present invention is formed in one step;
②分步热处理法：先将有机聚合物在400～1300℃下裂解；再进行600～1500℃下的金属氧化物的热还原；通过两步热处理制成本发明所指材料。② Step-by-step heat treatment method: first crack the organic polymer at 400-1300°C; then carry out thermal reduction of metal oxides at 600-1500°C; make the material referred to in the present invention through two-step heat treatment.
按本发明所得的锂离子电池负极材料有较碳负极材料高得多的可逆储锂容量，其值高达500mA/g。The lithium ion battery negative electrode material obtained according to the invention has a much higher reversible lithium storage capacity than the carbon negative electrode material, and its value is as high as 500mA/g.
所得负极材料的可逆储锂容量的测试方法如下：The test method of the reversible lithium storage capacity of gained negative electrode material is as follows:
在无水无氧的氩气箱中将上述所得负极材料与金属锂片组装成电池，该电池采用的隔膜为多孔多层PP/PE/PP膜、电解液为1MLiPF6的EC+DEC(体积比1∶1)，电池在0-2.0V的范围内充放电，充放电的电流恒定为100mA/g。In an anhydrous and oxygen-free argon gas box, the above-mentioned negative electrode material and metal lithium sheet are assembled into a battery. The separator used in the battery is a porous multilayer PP/PE/PP film, and the electrolyte is 1MLiPF EC+DEC (volume ratio 1:1), the battery is charged and discharged within the range of 0-2.0V, and the charge and discharge current is constant at 100mA/g.
本发明的优点：Advantages of the present invention:
1.发挥金属或合金的安全和高容量的特点，是目前最佳的锂离子电池负极材料。1. Taking advantage of the safety and high capacity of metals or alloys, it is currently the best negative electrode material for lithium-ion batteries.
2.采用活性材料纳米化，解决了金属或合金作为负极材料的在循环过程中的粉化问题；同时采用碳基材对活性材料颗粒的定域处理，解决了纳米活性材料的循环过程中的聚集问题；本发明改善了金属或合金作为负极材料的电化学循环性能，使其实用于电池的生产。2. The use of nanonization of active materials solves the problem of pulverization of metals or alloys as negative electrode materials during the cycle; at the same time, the use of carbon substrates for localized treatment of active material particles solves the problem of nano-active materials in the cycle process. Aggregation problem; the invention improves the electrochemical cycle performance of the metal or alloy as the negative electrode material, making it applicable to the production of batteries.
3.采用纳米金属氧化物的有机聚合物为原料，原辅材料易得，过程操作方便；3. Using organic polymers of nanometer metal oxides as raw materials, the raw and auxiliary materials are easy to obtain, and the process is easy to operate;
4.碳化和还原步骤可操作性强，工艺流程简便；4. The carbonization and reduction steps are highly operable and the process is simple;
5.碳基材具有特殊的结构，其中的分布广泛的介孔通道有利于锂离子的传输。5. The carbon substrate has a special structure in which the widely distributed mesoporous channels are conducive to the transmission of lithium ions.
总之满足了生产具有能量密度大、循环寿命长、自放电小、无记忆效应、性能优良的锂离子电池的要求。推动着锂离子电池用金属或合金负极材料的规模化生产和应用。In a word, it meets the requirements of producing lithium-ion batteries with high energy density, long cycle life, small self-discharge, no memory effect and excellent performance. Promote the large-scale production and application of metal or alloy anode materials for lithium-ion batteries.
具体实施方式：Detailed ways:
实施例1：Example 1:
在超声波作用下，将纳米SnO2分散于含50％氧化物量的酚醛树脂酒精溶液中，混合物以薄浆为宜；蒸干、干燥；置于N2保护炉中，升温至550℃保持3小时；后再升温至950℃，保持2小时；降温冷却；破碎过500目筛。得成品，测定材料初始电容量为563mAh/g，不可逆电容量为36mAh/g；循环10次后的电容量为486mAh/g。Under the action of ultrasonic waves, disperse the nano- SnO2 in the phenolic resin alcohol solution containing 50% oxides, the mixture is preferably grout; evaporate to dryness, dry; place in a N2 protection furnace, raise the temperature to 550 ° C for 3 hours ; Then raise the temperature to 950 ° C and keep it for 2 hours; cool down and cool; crush and pass through a 500-mesh sieve. The finished product was obtained, and the measured initial capacity of the material was 563mAh/g, and the irreversible capacity was 36mAh/g; the capacity after 10 cycles was 486mAh/g.
实施例2：Example 2:
在超声波作用下，将纳米(Sn，Sb)Ox分散于含40％氧化物量的酚醛树脂酒精溶液中，混合物以薄浆为宜；蒸干、干燥；置于N2保护炉中，升温至600℃保持3小时；后再升温至1000℃，保持2小时；降温冷却；破碎过300目筛。得成品，测定材料初始可逆电容量为510mAh/g，不可逆是容量为41mAh/g；循环10次后的电容量为493mAh/g。Under the action of ultrasonic waves, nanometer (Sn, Sb) O x is dispersed in the phenolic resin alcohol solution that contains 40% oxide content, and the mixture is advisable with grout; Evaporate to dryness, dry; Place N in protective furnace, heat up to Keep at 600°C for 3 hours; then raise the temperature to 1000°C and keep for 2 hours; cool down; crush through a 300-mesh sieve. The finished product was obtained, and the initial reversible capacity of the material was determined to be 510mAh/g, and the irreversible capacity was 41mAh/g; the capacity after 10 cycles was 493mAh/g.
实施例3：Example 3:
在超声波作用下，将纳米(Sn，Sb)Ox分散于含30％氧化物量的酚醛树脂酒精溶液中，混合物以薄浆为宜；蒸干、干燥；置于N2保护炉中，升温至600℃保持2小时；后再升温至1000℃，保持2小时；降温冷却；破碎过300目筛。得成品，测定材料初始可逆电容量为530mAh/g，不可逆容量为62mAh/g；循环10次后的电容量为497mAh/g。Under the action of ultrasonic waves, nanometer (Sn, Sb) O x is dispersed in the phenolic resin alcohol solution that contains 30% oxide content, and the mixture is advisable with grout; Evaporate to dryness, dry; Place N in protective furnace, heat up to Keep at 600°C for 2 hours; then raise the temperature to 1000°C and keep for 2 hours; cool down; crush through a 300-mesh sieve. The finished product was obtained, and the initial reversible capacitance of the material was measured to be 530mAh/g, and the irreversible capacity was 62mAh/g; the capacitance after 10 cycles was 497mAh/g.
实施例4：Example 4:
在超声波作用下，将纳米(Sn，Sb)Ox分散于含50％氧化物量的酚醛树脂酒精溶液中，混合物以薄浆为宜；蒸干、干燥；置于N2保护炉中，升温至650℃保持3小时；后再升温至1050℃，保持2小时；降温冷却；破碎过300目筛。得成品，测定材料初始可逆电容量为494mAh/g，不可逆容量为29mAh/g；循环10次后的电容量为477mAh/g。Under the action of ultrasonic waves, nano (Sn, Sb) O x is dispersed in the phenolic resin alcohol solution containing 50% oxide content, and the mixture is preferably a thin slurry; evaporated to dryness and dried; placed in N 2 protection furnace, heated to Keep at 650°C for 3 hours; then raise the temperature to 1050°C and keep for 2 hours; cool down; crush through a 300-mesh sieve. The finished product was obtained, and the measured initial reversible capacity of the material was 494mAh/g, and the irreversible capacity was 29mAh/g; the capacity after 10 cycles was 477mAh/g.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021546541A CN1231985C (en) | 2002-11-30 | 2002-11-30 | Composite nano metallic negative electrode material for lithium ion battery and method for making same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021546541A CN1231985C (en) | 2002-11-30 | 2002-11-30 | Composite nano metallic negative electrode material for lithium ion battery and method for making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1505188A true CN1505188A (en) | 2004-06-16 |
| CN1231985C CN1231985C (en) | 2005-12-14 |
Family
ID=34235544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021546541A Expired - Fee Related CN1231985C (en) | 2002-11-30 | 2002-11-30 | Composite nano metallic negative electrode material for lithium ion battery and method for making same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1231985C (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301560C (en) * | 2005-05-08 | 2007-02-21 | 北京科技大学 | Method of preparing Sn-Sb alloy material for negative electrode of lithium ion cell |
| CN100341172C (en) * | 2005-09-15 | 2007-10-03 | 复旦大学 | Film lithium ion battery using stannous selenide film as anode material and its preparation method |
| CN100373664C (en) * | 2006-04-07 | 2008-03-05 | 北京科技大学 | Preparation method of high-capacity tin-nickel alloy composite lithium-ion battery negative electrode material |
| CN100376050C (en) * | 2006-05-24 | 2008-03-19 | 天津大学 | Lithium-ion battery anode material |
| CN100446309C (en) * | 2007-05-23 | 2008-12-24 | 福建师范大学 | Preparation method capable of controlling particle size of tin-copper-nickel-cobalt alloy negative electrode material |
| CN101908617A (en) * | 2009-06-05 | 2010-12-08 | 株式会社神户制钢所 | Negative electrode material for lithium ion secondary battery, method for producing same, and lithium ion secondary battery |
| CN101908618A (en) * | 2009-06-08 | 2010-12-08 | 株式会社神户制钢所 | Negative electrode material for lithium ion secondary battery, method for producing same, and lithium ion secondary battery |
| CN102102198A (en) * | 2011-02-12 | 2011-06-22 | 南京大学 | Method for regulating distribution of metal nano granules in resin carrier |
| CN101601162B (en) * | 2006-08-09 | 2012-01-04 | 丰田自动车工程及制造北美公司 | High-performance anode materials for lithium-ion batteries |
| WO2012119562A1 (en) * | 2011-03-10 | 2012-09-13 | 丰田自动车株式会社 | Tin carbon composite, method for preparing same, battery negative electrode component comprising same, and battery having the negative electrode component |
| CN101752554B (en) * | 2010-01-04 | 2012-12-19 | 北京航空航天大学 | Method for preparing Sn-Zn alloy cathode material of lithium ion battery |
| CN103460454A (en) * | 2011-03-30 | 2013-12-18 | 日本贵弥功株式会社 | Negative electrode active material, method for producing the negative electrode active material, and lithium ion secondary battery using the negative electrode active material |
| CN104541392A (en) * | 2012-06-18 | 2015-04-22 | 赫罗伊斯石英玻璃股份有限两合公司 | Process for producing composite powder and for porous composite material produced using the composite powder for electrochemical electrodes |
| CN106129361A (en) * | 2016-07-25 | 2016-11-16 | 北京化工大学 | A kind of lithium ion battery anode active material and preparation method |
| CN108539185A (en) * | 2018-05-24 | 2018-09-14 | 中南大学 | A kind of lithium or anode material of lithium-ion battery and preparation method thereof |
| CN108671924A (en) * | 2018-05-24 | 2018-10-19 | 中南大学 | A kind of nano metal/carbon composite and its preparation method and application |
| CN108977684A (en) * | 2018-08-01 | 2018-12-11 | 常州市金坛磁性材料有限公司 | A kind of soft magnetism CoCuC composite material and preparation method |
| CN110350216A (en) * | 2019-06-26 | 2019-10-18 | 郭峰 | A kind of preparation method of cathode in direct methanol fuel cells support body material |
| CN114975847A (en) * | 2022-07-07 | 2022-08-30 | 中南大学 | A composite metal negative electrode with sandwich structure and its preparation method and application |
-
2002
- 2002-11-30 CN CNB021546541A patent/CN1231985C/en not_active Expired - Fee Related
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301560C (en) * | 2005-05-08 | 2007-02-21 | 北京科技大学 | Method of preparing Sn-Sb alloy material for negative electrode of lithium ion cell |
| CN100341172C (en) * | 2005-09-15 | 2007-10-03 | 复旦大学 | Film lithium ion battery using stannous selenide film as anode material and its preparation method |
| CN100373664C (en) * | 2006-04-07 | 2008-03-05 | 北京科技大学 | Preparation method of high-capacity tin-nickel alloy composite lithium-ion battery negative electrode material |
| CN100376050C (en) * | 2006-05-24 | 2008-03-19 | 天津大学 | Lithium-ion battery anode material |
| CN101601162B (en) * | 2006-08-09 | 2012-01-04 | 丰田自动车工程及制造北美公司 | High-performance anode materials for lithium-ion batteries |
| CN100446309C (en) * | 2007-05-23 | 2008-12-24 | 福建师范大学 | Preparation method capable of controlling particle size of tin-copper-nickel-cobalt alloy negative electrode material |
| CN101908617A (en) * | 2009-06-05 | 2010-12-08 | 株式会社神户制钢所 | Negative electrode material for lithium ion secondary battery, method for producing same, and lithium ion secondary battery |
| CN101908618A (en) * | 2009-06-08 | 2010-12-08 | 株式会社神户制钢所 | Negative electrode material for lithium ion secondary battery, method for producing same, and lithium ion secondary battery |
| CN101752554B (en) * | 2010-01-04 | 2012-12-19 | 北京航空航天大学 | Method for preparing Sn-Zn alloy cathode material of lithium ion battery |
| CN102102198A (en) * | 2011-02-12 | 2011-06-22 | 南京大学 | Method for regulating distribution of metal nano granules in resin carrier |
| CN102102198B (en) * | 2011-02-12 | 2013-08-07 | 南京大学 | Method for regulating distribution of metal nano granules in resin carrier |
| JP2014512635A (en) * | 2011-03-10 | 2014-05-22 | トヨタ自動車株式会社 | A composite of tin and carbon, a method for producing the same, a battery negative electrode material containing the composite, and a battery including the negative electrode material |
| CN102683654A (en) * | 2011-03-10 | 2012-09-19 | 丰田自动车株式会社 | Tin carbon composite, preparation method thereof, battery anode part comprising tin carbon composite, and battery with anode part |
| WO2012119562A1 (en) * | 2011-03-10 | 2012-09-13 | 丰田自动车株式会社 | Tin carbon composite, method for preparing same, battery negative electrode component comprising same, and battery having the negative electrode component |
| CN103460454A (en) * | 2011-03-30 | 2013-12-18 | 日本贵弥功株式会社 | Negative electrode active material, method for producing the negative electrode active material, and lithium ion secondary battery using the negative electrode active material |
| CN103460454B (en) * | 2011-03-30 | 2016-10-26 | 日本贵弥功株式会社 | Negative electrode active material, method for producing the negative electrode active material, and lithium ion secondary battery using the negative electrode active material |
| CN104541392A (en) * | 2012-06-18 | 2015-04-22 | 赫罗伊斯石英玻璃股份有限两合公司 | Process for producing composite powder and for porous composite material produced using the composite powder for electrochemical electrodes |
| CN104541392B (en) * | 2012-06-18 | 2016-12-07 | 赫罗伊斯石英玻璃股份有限两合公司 | For producing composite powder and for the composite porous method for electrochemical electrode using this composite powder to produce |
| CN106129361A (en) * | 2016-07-25 | 2016-11-16 | 北京化工大学 | A kind of lithium ion battery anode active material and preparation method |
| CN106129361B (en) * | 2016-07-25 | 2018-07-27 | 北京化工大学 | A kind of lithium ion battery anode active material and preparation method |
| CN108539185A (en) * | 2018-05-24 | 2018-09-14 | 中南大学 | A kind of lithium or anode material of lithium-ion battery and preparation method thereof |
| CN108671924A (en) * | 2018-05-24 | 2018-10-19 | 中南大学 | A kind of nano metal/carbon composite and its preparation method and application |
| CN108671924B (en) * | 2018-05-24 | 2020-06-16 | 中南大学 | Nano metal/carbon composite material and preparation method and application thereof |
| CN108539185B (en) * | 2018-05-24 | 2020-12-15 | 中南大学 | A kind of lithium or sodium ion battery negative electrode material and preparation method thereof |
| CN108977684A (en) * | 2018-08-01 | 2018-12-11 | 常州市金坛磁性材料有限公司 | A kind of soft magnetism CoCuC composite material and preparation method |
| CN110350216A (en) * | 2019-06-26 | 2019-10-18 | 郭峰 | A kind of preparation method of cathode in direct methanol fuel cells support body material |
| CN114975847A (en) * | 2022-07-07 | 2022-08-30 | 中南大学 | A composite metal negative electrode with sandwich structure and its preparation method and application |
| CN114975847B (en) * | 2022-07-07 | 2024-02-27 | 中南大学 | Composite metal negative electrode with sandwich structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1231985C (en) | 2005-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1231985C (en) | Composite nano metallic negative electrode material for lithium ion battery and method for making same | |
| CN105206801B (en) | A kind of preparation method of silicon-carbon composite anode material for lithium ion battery | |
| CN100347887C (en) | Composite graphite negative electrode material for lithium ion secondary cell and its preparation method | |
| CN102130323B (en) | Lithium ion battery film cathode containing porous polymer elastomer and preparation method thereof | |
| CN111470486A (en) | Three-dimensional silicon-carbon composite negative electrode material, preparation method thereof and application thereof in lithium ion battery | |
| CN104577081A (en) | Anode material for lithium-ion battery and preparation method of anode material | |
| CN105047888B (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| WO2016008455A2 (en) | Multiple-element composite material for negative electrodes, preparation method therefor, and lithium-ion battery having same | |
| WO2023273726A1 (en) | Negative electrode material, preparation method therefor, and lithium ion battery | |
| CN102306783A (en) | Multi-layer graphene/lithium iron phosphate intercalated composite material, preparation method thereof, and lithium ion battery adopting multi-layer grapheme/lithium iron phosphate intercalated composite material as anode material | |
| CN104218216B (en) | Molybdenum disulfide nanocomposite negative electrode material, and preparation method and use thereof | |
| CN102522561A (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN108682813A (en) | A kind of preparation method and application of Si-C composite material | |
| CN106784833A (en) | Silicon-carbon cathode material and preparation method thereof | |
| CN110550635B (en) | Preparation method of novel carbon-coated silica negative electrode material | |
| CN115692647B (en) | Carbon-coated and exfoliated metal sulfide composite graphite nanosheet battery anode material and its preparation method | |
| CN103337634A (en) | Graphite cathode material coated with conductive titanium nitride network membrane on the surface and preparation method of the graphite cathode material | |
| WO2023083147A1 (en) | Negative electrode active material, negative electrode plate comprising negative electrode active material, and lithium ion battery | |
| CN1305150C (en) | Modified graphite and its preparing method | |
| CN1315207C (en) | Composite negative pole material of Li-ion battery and its preparing process | |
| CN116332154A (en) | Preparation method of porous silicon-carbon anode material | |
| CN115224241A (en) | Negative plate for lithium battery and preparation method and application thereof | |
| Wang et al. | Dual‐functional and polydopamine‐coated vanadium disulfide for “fast‐charging” lithium‐ion batteries | |
| CN105870435A (en) | A kind of MoO2@CNTs composite material and its preparation method | |
| CN1850597A (en) | Method for preparig lithium secondary cell silicon/rich-lithium phase composite cathode material by high energy ball milling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |