CN102629685B - Preparation method of Cu2O/Cu/PPy nanowire composite lithium ion battery negative material - Google Patents
Preparation method of Cu2O/Cu/PPy nanowire composite lithium ion battery negative material Download PDFInfo
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- CN102629685B CN102629685B CN201210103658.6A CN201210103658A CN102629685B CN 102629685 B CN102629685 B CN 102629685B CN 201210103658 A CN201210103658 A CN 201210103658A CN 102629685 B CN102629685 B CN 102629685B
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Abstract
The invention relates to a preparation method of a Cu2O/Cu/PPy nanowire composite lithium ion battery negative material. The preparation method comprises the following steps of: (1) preparing pyrrole monomer solution and copper acetate solution and performing ultrasonic treatment to uniformly disperse the solution; (2) mixing the pyrrole monomer solution and the copper acetate solution obtained by the step (1) according to a volume ratio of 1:13-1:3 and transferring into a hydrothermal reaction kettle; (3) placing the hydrothermal reaction kettle in a drying oven to react for 10-20 hours, wherein the temperature of the drying oven is 120-180 DEG C; and (4) centrifugally separating a product obtained by the reaction, washing and then drying to obtain the Cu2O/Cu/PPy nanowire composite lithium ion battery negative material. Compared with the prior art, the material obtained by the invention has higher specific capacity compared with that of the lithium ion battery negative material and has good cycle performance.
Description
Technical field
The invention belongs to energy storage material preparing technical field, be specifically related to the Cu of a kind of height ratio capacity and high cycle performance
2the preparation method of the nanometer wire lithium ion battery negative material that O/Cu/PPy is compound.
Background technology
Due to the exhaustion day by day of the energy, add the day by day serious of municipal pollution, people are day by day urgent to the demand of novel green high efficient energy sources, and lithium ion battery becomes research emphasis now as the new forms of energy with powerful advantages.It has many outstanding advantages: lightweight, energy storage is large, power is large, pollution-free, also non-secondary pollution, life-span are long, self discharge coefficient is little, temperature accommodation is wide.
At present, the negative material that lithium ion battery is used is all generally material with carbon element, as graphite, soft carbon (as coke etc.), hard carbon etc.Although carbon negative pole material is successful commercialization, but still the weakness that exists some to be difficult to overcome, for example the compatible ability of graphite-like material with carbon element and organic solvent is poor, solvent easily occurs and embed altogether, reduces embedding lithium performance; Lithium ion diffusion coefficient in graphite is little, is unfavorable for fast charging and discharging; The current potential of carbon negative pole and the current potential of lithium metal are very approaching, the easy precipitating metal lithium of carbon electrodes when over-charging of battery and cause short circuit; At high temperature, the protective layer on carbon negative pole may decompose and cause battery to catch fire; In addition, carbon negative pole theoretical capacity is only 372mAh/g, can not fully meet the requirement of high power capacity, high power density lithium ion battery.
The non-carbon negative pole material of report has nitride, lithium iron compound oxide, tin-based material, silica-base material, transition metal oxide and some other novel alloy material etc. in recent years.Wherein as lithium ion battery negative material, to have outstanding chemical property be up-and-coming lithium ion battery negative material to the 3d transition metal oxide of nano-scale (MO, M is Co, Ni, Cu, Fe).
Nano transition metal oxides Cu
2o is because its higher energy density and good high rate performance become the focus of people's research.Nanometer Cu
2o is a kind of typical p-type semiconductor, and energy gap is 2.17eV, is not only expected to become outstanding lithium ion battery negative material, and at solar energy converter and solar cell, transducer, magnetic memory, superconductor, the fields such as photochemical catalyst and biology sensor have broad application prospects.In the past few years, researcher has reported the nanometer Cu of a lot of structures
2o, as structures such as cube shaped, octahedral build, hollow structure and nano wires.The Cu of per unit in theory
2o can with two Li
+carry out reversible reaction, Cu between 0.2-3V
2the theoretical capacity of O reaches 400mAhg
-1.A lot of researchers are Cu
2o is as carbon negative electrode material of lithium ion cell substitute.Yet, Cu
2o is that p-type semiconductor, conductivity are not high, and this has caused Cu
2the actual specific capacity of O is far smaller than theoretical capacity.
In recent years, the composite material of polypyrrole (PPy) and inorganic micro Nano material more and more causes scientists and engineers' broad interest with its excellent physics, chemical property and wide application prospect.After PPy and inorganic nano material are compound, material is all made moderate progress at aspects such as mechanical property, environmental stability, machinabilitys, the conductivity of material, magnetic conductivity, microwave absorption are also all had clear improvement.
Summary of the invention
Object of the present invention is exactly that the Cu of a kind of height ratio capacity and high cycle performance is provided in order to overcome the defect of above-mentioned prior art existence
2the preparation method of O/Cu/PPy nano wire composite lithium ion battery cathode material.
Object of the present invention can be achieved through the following technical solutions: a kind of Cu
2the preparation method of O/Cu/PPy nano wire composite lithium ion battery cathode material, is characterized in that, comprises the following steps:
(1) preparation pyrrole monomer solution and copper acetate solution, is ultrasonicly uniformly dispersed it;
(2) be 1 by volume: 13-1: 3 measure the pyrrole monomer solution that step (1) obtains mixes with copper acetate solution, and transfers in hydrothermal reaction kettle;
(3) hydrothermal reaction kettle is placed in baking oven, it is 120-180 ℃ that oven temperature is set, reaction 10-20h;
(4) product reaction being obtained carries out centrifugation, after washing, is dried processing, obtains Cu
2o/Cu/PPy nano wire composite lithium ion battery cathode material.
The concentration of the pyrrole monomer solution that step (1) is described is 0.1-0.2mol/L.
The concentration of the copper acetate solution that step (1) is described is 0.05mol/L.
The described dry processing of step (4) refers to: in the drying box of 40-60 ℃, and dry 5-12h.
Compared with prior art, the present invention is by adopting pyrrole and cupric to react the Cu that has prepared nanometer linear structure under certain condition
2o/Cu/PPy nano wire negative material, by the Cu obtaining
2o/Cu/PPy set of nanowires is dressed up fastening lithium ionic cell, carries out Electrical Analysis sign, and through test, specific capacity, at 0.2C, when 0.5C and 1C multiplying power, reaches 635mAh/g, 600mAh/g and 540mAh/g, and in 300 circulations not decay afterwards.Can find out, this material has higher specific capacity as lithium ion battery negative material, and have good cycle performance, for improving cycle performance and the capacity of lithium ion battery negative material, the lithium ion battery that obtains height ratio capacity has important theory and practice meaning.
Accompanying drawing explanation
Fig. 1 is Cu
2the stereoscan photograph of O/Cu/PPy nano wire;
Fig. 2 is Cu
2the XRD diffracting spectrum of O/Cu/PPy nano wire;
Fig. 3 is Cu
2o/Cu/PPy nano wire is dressed up the cyclic voltammetry situation after button cell;
Fig. 4 is Cu
2o/Cu/PPy nano wire is dressed up after button cell charge-discharge test situation under different multiplying.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Preparation the pyrrole monomer solution of 0.1mol/L and the copper acetate solution of 0.05mol/L, be ultrasonicly uniformly dispersed it.Get the copper acetate solution that pyrrole monomer solution that 10mL prepares prepares with 65mL and mix, and transfer in hydrothermal reaction kettle; Hydrothermal reaction kettle is placed in baking oven, is 160 ℃ by Temperature Setting, reaction 12h; The product that reaction is obtained carries out centrifuge washing, and is dried 12h at 50 ℃, by the Cu obtaining
2o/Cu/PPy set of nanowires is dressed up fastening lithium ionic cell, carries out Electrical Analysis sign.
Gained Cu
2the stereoscan photograph of O/Cu/PPy nano wire, as shown in Figure 1; Cu
2the XRD diffracting spectrum of O/Cu/PPy nano wire, as shown in Figure 2; Cu
2o/Cu/PPy nano wire is dressed up the cyclic voltammetry situation after button cell, as shown in Figure 3; Cu
2o/Cu/PPy nano wire is dressed up after button cell charge-discharge test situation under different multiplying, as shown in Figure 4.Can find out the Cu that the inventive method makes
2o/Cu/PPy nano wire, is proved and can greatly improves electron conduction ability through performance characterization, specific capacity is had significantly and increase.Through loop test, specific capacity, at 0.2C, when 0.5C and 1C multiplying power, reaches 635mAh/g, 600mAh/g and 540mAh/g, and in 300 circulations not decay afterwards.
Embodiment 2
Preparation the pyrrole monomer solution of 0.2mol/L and the copper acetate solution of 0.05mol/L, be ultrasonicly uniformly dispersed it.Get the copper acetate solution that pyrrole monomer solution that 16.25mL prepares prepares with 65mL and mix, and transfer in hydrothermal reaction kettle; Hydrothermal reaction kettle is placed in baking oven, is 140 ℃ by Temperature Setting, reaction 15h; The product that reaction is obtained carries out centrifuge washing, and is dried 12h at 50 ℃, by the Cu obtaining
2o/Cu/PPy set of nanowires is dressed up fastening lithium ionic cell, carries out Electrical Analysis sign.
Embodiment 3
Preparation the pyrrole monomer solution of 0.2mol/L and the copper acetate solution of 0.05mol/L, be ultrasonicly uniformly dispersed it.
Get the copper acetate solution that pyrrole monomer solution that 13.5mL prepares prepares with 65mL and mix, and transfer in hydrothermal reaction kettle; Hydrothermal reaction kettle is placed in baking oven, is 130 ℃ by Temperature Setting, reaction 20h; The product that reaction is obtained carries out centrifuge washing, and is dried 12h at 50 ℃, by the Cu obtaining
2o/Cu/PPy set of nanowires is dressed up fastening lithium ionic cell, carries out Electrical Analysis sign.
Embodiment 4
Preparation the pyrrole monomer solution of 0.1mol/L and the copper acetate solution of 0.05mol/L, be ultrasonicly uniformly dispersed it.Get the copper acetate solution that pyrrole monomer solution that 5mL prepares prepares with 65mL and mix, and transfer in hydrothermal reaction kettle; Hydrothermal reaction kettle is placed in baking oven, is 120 ℃ by Temperature Setting, reaction 20h; The product that reaction is obtained carries out centrifuge washing, and is dried 5h at 60 ℃, by the Cu obtaining
2o/Cu/PPy set of nanowires is dressed up fastening lithium ionic cell, carries out Electrical Analysis sign.
Embodiment 5
Preparation the pyrrole monomer solution of 0.1mol/L and the copper acetate solution of 0.05mol/L, be ultrasonicly uniformly dispersed it.Get the copper acetate solution that pyrrole monomer solution that 10mL prepares prepares with 30mL and mix, and transfer in hydrothermal reaction kettle; Hydrothermal reaction kettle is placed in baking oven, is 180 ℃ by Temperature Setting, reaction 10h; The product that reaction is obtained carries out centrifuge washing, and is dried 12h at 40 ℃, by the Cu obtaining
2o/Cu/PPy set of nanowires is dressed up fastening lithium ionic cell, carries out Electrical Analysis sign.
Claims (2)
1. a Cu
2the preparation method of O/Cu/PPy nano wire composite lithium ion battery cathode material, is characterized in that, comprises the following steps:
(1) preparation pyrrole monomer solution and copper acetate solution, is ultrasonicly uniformly dispersed it;
(2) for 1:13-1:3 measures the pyrrole monomer solution that step (1) obtains, mix with copper acetate solution by volume, and transfer in hydrothermal reaction kettle;
(3) hydrothermal reaction kettle is placed in baking oven, it is 120-180 ℃ that oven temperature is set, reaction 10-20h;
(4) product reaction being obtained carries out centrifugation, after washing, is dried processing, obtains Cu
2o/Cu/PPy nano wire composite lithium ion battery cathode material;
The concentration of the pyrrole monomer solution that step (1) is described is 0.1-0.2mol/L;
The concentration of the copper acetate solution that step (1) is described is 0.05mol/L.
2. a kind of Cu according to claim 1
2the preparation method of O/Cu/PPy nano wire composite lithium ion battery cathode material, is characterized in that, the described dry processing of step (4) refers to: in the drying box of 40-60 ℃, and dry 5-12h.
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| CN111082066A (en) * | 2019-12-25 | 2020-04-28 | 山东大学 | Three-dimensional lithium-philic conductive network material, preparation method and application |
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| CN103474258B (en) * | 2013-09-16 | 2016-04-20 | 哈尔滨工程大学 | A kind of nickel foam carries Cu/Cu 2the preparation method of the electrode material for super capacitor of O |
| CN108054362A (en) * | 2017-12-11 | 2018-05-18 | 宁波高新区锦众信息科技有限公司 | A kind of preparation method of lithium ion battery copper oxide composite negative pole material |
| CN109256556B (en) * | 2018-10-19 | 2020-11-17 | 陕西科技大学 | Cross star-shaped Cu/Cu with core-shell structure2O/CuO @ Ppy composite material and preparation method and application thereof |
| CN109820001B (en) * | 2019-02-18 | 2023-11-17 | 江苏理工学院 | Cu (copper) alloy 2 Preparation method of O/ZnO composite nano material and application of material |
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| CN101525436B (en) * | 2009-03-20 | 2011-05-25 | 西北师范大学 | Polypyrrole/Fe*O*/nanometer graphite sheet composite material and preparation method thereof |
| CN102315420B (en) * | 2010-07-05 | 2014-09-10 | 中国科学院上海硅酸盐研究所 | Metal cathode structure with protection layer and preparation method thereof |
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| CN111082066A (en) * | 2019-12-25 | 2020-04-28 | 山东大学 | Three-dimensional lithium-philic conductive network material, preparation method and application |
| CN111082066B (en) * | 2019-12-25 | 2020-12-22 | 山东大学 | Three-dimensional lithium-philic conductive network material, preparation method and application |
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Effective date of registration: 20200713 Address after: Room 601, gate 3, building 11, No. 6142 Renmin Street, Nanguan District, Changchun City, Jilin Province Co-patentee after: Qin Li Patentee after: Wang Lijun Co-patentee after: Song Junfeng Co-patentee after: Yang Minglai Address before: Group 471, xierhu Tongwei, Yan'an street, Hongqi Street, Chaoyang District, Changchun City, Jilin Province Patentee before: Qin Li Effective date of registration: 20200713 Address after: Group 471, xierhu Tongwei, Yan'an street, Hongqi Street, Chaoyang District, Changchun City, Jilin Province Patentee after: Qin Li Address before: 200240 Dongchuan Road, Shanghai, No. 800, No. Patentee before: SHANGHAI JIAO TONG University |
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Effective date of registration: 20200915 Address after: Room B255, block B, Dobe e e-Park, Dongxi, Pengbu street, Jianggan District, Hangzhou City, Zhejiang Province Patentee after: Zhejiang Changxin Photoelectric Technology Co.,Ltd. Address before: Room 601, gate 3, building 11, No. 6142 Renmin Street, Nanguan District, Changchun City, Jilin Province Co-patentee before: Qin Li Patentee before: Wang Lijun Co-patentee before: Song Junfeng Co-patentee before: Yang Minglai |