CN102916195B - Graphene-coated copper oxide composite cathode material and method for manufacturing same - Google Patents

Graphene-coated copper oxide composite cathode material and method for manufacturing same Download PDF

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CN102916195B
CN102916195B CN201210426228.8A CN201210426228A CN102916195B CN 102916195 B CN102916195 B CN 102916195B CN 201210426228 A CN201210426228 A CN 201210426228A CN 102916195 B CN102916195 B CN 102916195B
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graphene
solution
cupric oxide
oxide composite
sodium hydroxide
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CN102916195A (en
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黄正宏
丁翔
沈万慈
康飞宇
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Tsinghua University
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Tsinghua University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a graphene-coated copper oxide composite cathode material and a method for manufacturing the same. The graphene-coated copper oxide composite cathode material comprises, by mass, from 20% to 90% of copper oxide and from 10% to 80% of graphene. The method includes uniformly mixing copper salt solution and graphene oxide solution at first, and stirring the copper salt solution and the graphene oxide solution at a constant temperature for 15 minutes to 1 hour to obtain mixed solution; dripping sodium hydroxide solution into the mixed solution, continuously stirring the mixed solution added with the sodium hydroxide solution for 0.5 hour to 2 hours and allowing the mixed solution added with the sodium hydroxide solution to stand for 2 to 24 hours; and performing centrifuging and hydrothermal processing for the mixed solution added with the sodium hydroxide solution to obtain a product, and drying the product at the temperature of 120 DEG C for 12 hours to obtain the graphene-coated copper oxide composite cathode material. The graphene-coated copper oxide composite cathode material and the method have the advantages that the synthesis method is simple, the manufactured graphene-coated copper oxide composite cathode material is good in performance, and technical problems of poor conductivity of a copper oxide electrode and decrease of capacity due to gradual chalking in charge and discharge processes are solved.

Description

A kind of graphene coated cupric oxide composite negative pole material and preparation method thereof
Technical field
The invention belongs to lithium ion battery material technical field, be specifically related to a kind of graphene coated cupric oxide composite negative pole material and preparation method thereof.
Background technology
Along with current electronics miniaturization and microminiaturized develop rapidly, the research and apply of lithium ion battery is also more and more paid attention to.Lithium ion battery has been widely used in mobile phone, notebook computer, digital camera and portable small-sized electrical equipment and submarine, space flight, aviation field, and progressively moves towards the dynamic field such as electric automobile.But especially specific capacity is on the low side for current commercial graphite cathode limited capacity, lithium ion battery be made to realize real large-scale application in electric automobile field, also must improve the energy density of battery cathode, high rate during charging-discharging and cycle life.
Cupric oxide is the very potential lithium ion battery negative material of one, and theoretical capacity is 670mAhg -1, close to the twice of commercial graphite negative pole, and environmental pollution is little, with low cost.The shortcoming first of cupric oxide is low as p-type semiconductor conductivity, and electro-chemical activity is poor; Its two be exist in charge and discharge process about 174% change in volume, make the efflorescence gradually of copper oxide active material, lose electrical contact between active material and cause capacity to be decayed rapidly.Cupric oxide nano and Composite are two kinds of methods improving material property, and wherein with material with carbon element such as carbon nano-tube compound, composite material exhibits goes out good chemical property.
Summary of the invention
For solving the problems of the technologies described above, the present invention proposes a kind of graphene coated cupric oxide composite negative pole material and preparation method thereof, there is synthetic method simple, the graphene coated cupric oxide composite negative pole material performance of preparation is good, to solve in cupric oxide electrode conductivuty difference and charge and discharge process the efflorescence technical problem that causes capacity to reduce gradually.
To achieve these goals, the present invention adopts following technical scheme:
A kind of graphene coated cupric oxide composite negative pole material, in described material, the mass percentage content of cupric oxide is 20 ~ 90%, and the mass percentage content of Graphene is 10 ~ 80%.
In described material, Graphene presents sheet and is coated in the middle of lamella by cupric oxide.
The preparation method of graphene coated cupric oxide composite negative pole material described above, first the graphene oxide solution be copper salt solution and the concentration of 0.02 ~ 0.2mol/L by concentration being 0.05 ~ 1mol/L mixes constant temperature and stirs 15min ~ 1h, obtain mixed solution, the mass ratio of described copper salt solution and graphene oxide solution is 1: 2 ~ 2: 1; Then be place 2 ~ 24h after the sodium hydroxide solution Keep agitation 0.5 ~ 2h of 0.1 ~ 0.2mol/L to mixed solution and dripping concentration, the mass percent that the dripping quantity of described sodium hydroxide solution accounts for mixed solution is 20 ~ 30%; Carry out centrifugal and hydro-thermal subsequently, the product obtained dries 12h at 120 DEG C, obtains graphene coated cupric oxide composite negative pole material.
Described mantoquita is copper chloride, copper nitrate, copper sulphate or Schweinfurt green.
Described sodium hydroxide solution can replace with potassium hydroxide or ammoniacal liquor.
Described lasting constant temperature stirs and adopts water bath with thermostatic control mode, and bath temperature is 20 ~ 80 DEG C.
Described hydro-thermal adopts microwave radiation technology hydro-thermal, and hydrothermal temperature is 160 ~ 220 DEG C, and the hydro-thermal time is 15min ~ 2h.
Adopt technique scheme, a kind of graphene coated cupric oxide composite negative pole material provided by the present invention and preparation method thereof.In graphene coated cupric oxide composite negative pole material, cupric oxide effectively prevents the reunion of Graphene, the three-dimensional conductive network that Graphene is formed simultaneously accelerates the migration of electronics, and for cupric oxide volumetric expansion shrink reserved enough spaces, effectively alleviate the efflorescence of cupric oxide, composite material chemical property has had remarkable lifting relative to one-component.Have synthetic method simple, the graphene coated cupric oxide composite negative pole material performance of preparation is good, to solve in cupric oxide electrode conductivuty difference and charge and discharge process the technical problem that efflorescence gradually causes capacity to reduce.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of the composite material that example 1 of the present invention obtains.
Fig. 2 is the SEM picture of the composite material that example 1 of the present invention obtains.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described further.
Embodiment one
Take the CuCl of 1.7g 22H 2o is dissolved in deionized water and is made into the copper chloride solution that concentration is 0.1mol/L, be that (concentration of graphene oxide solution is demarcated in advance for the graphene oxide solution of 0.17mol/L with 100ml concentration, in solution, Graphene quality is about the half of graphene oxide quality) mix and stir 30min, keep water bath with thermostatic control, temperature is set as 50 DEG C, and dropping concentration is that the sodium hydroxide solution 120ml of 0.2mol/L continues constant temperature stirring 1h; Centrifugal after placing 8h, adopt microwave radiation technology hydro-thermal subsequently, hydrothermal temperature is 180 DEG C, and the hydro-thermal time is 1h; Dry 12h, obtain graphene coated cupric oxide composite negative pole material for last 120 DEG C.
In the graphene coated cupric oxide composite negative pole material that the present embodiment obtains, the mass percentage content of cupric oxide is 80%, and the mass percentage content of Graphene is 20%.The XRD collection of illustrative plates of obtained composite material and SEM picture are as depicted in figs. 1 and 2.
Embodiment two
Take the Cu (NO of 2.7g 3) 23H 2o is dissolved in deionized water and is made into the copper nitrate solution that concentration is 0.113mol/L, the graphene oxide solution being 0.083mol/L with 100ml concentration mixes and stirs 15min, keep water bath with thermostatic control, temperature is set as 30 DEG C, and dropping concentration is that the sodium hydroxide solution 140ml of 0.2mol/L continues constant temperature stirring 2h; Centrifugal after placing 4h, adopt microwave radiation technology hydro-thermal subsequently, hydrothermal temperature is 160 DEG C, and the hydro-thermal time is 30min; Dry 12h, obtain graphene coated cupric oxide composite negative pole material for last 120 DEG C.
In the graphene coated cupric oxide composite negative pole material that the present embodiment obtains, the mass percentage content of cupric oxide is 90%, and the mass percentage content of Graphene is 10%.
Embodiment three
Take the Cu (SO of 1.9g 4) 25H 2o is dissolved in deionized water and is made into the copper-bath that concentration is 0.075mol/L, the graphene oxide solution being 0.333mol/L with 100ml concentration mixes and stirs 1h, keep water bath with thermostatic control, temperature is set as 60 DEG C, and dropping concentration is that the potassium hydroxide solution 90ml of 0.2mol/L continues constant temperature stirring 1.5h; Centrifugal after placing 12h, adopt microwave radiation technology hydro-thermal subsequently, hydrothermal temperature is 200 DEG C, and the hydro-thermal time is 2h.Dry 12h, obtain graphene coated cupric oxide composite negative pole material for last 120 DEG C.
In the graphene coated cupric oxide composite negative pole material that the present embodiment obtains, the mass percentage content of cupric oxide is 60%, and the mass percentage content of Graphene is 40%.
Embodiment four
Take the Cu (CH3COO) of 500mg 2h 2o is dissolved in deionized water and is made into the Schweinfurt green solution that concentration is 0.038mol/L, the graphene oxide solution being 0.667mol/L with 100ml concentration mixes and stirs 45min, keep water bath with thermostatic control, temperature is set as 80 DEG C, and dripping concentration is that 30% ammonia spirit 20ml continues constant temperature stirring 30min; Centrifugal after placing 24h, adopt microwave radiation technology hydro-thermal subsequently, hydrothermal temperature is 220 DEG C, and the hydro-thermal time is 1.5h.Dry 12h, obtain graphene coated cupric oxide composite negative pole material for last 120 DEG C.
In the graphene coated cupric oxide composite negative pole material that the present embodiment obtains, the mass percentage content of cupric oxide is 20%, and the mass percentage content of Graphene is 80%.
Further electro-chemical test is as follows:
1. the preparation of battery: 30mg cupric oxide/graphene composite material, 2mg conductive black and 8mg segregation PVF (PVDF) are mixed, add to be dissolved in right amount in 1-METHYLPYRROLIDONE (NMP) and fully grind furnishing thickener, with scraper, it is evenly coated on Copper Foil.80 DEG C dry roughly after to be become by Copper Foil stamping-out diameter to be the disk of 10mm, use roll squeezer by diaphragm compacting, continue to put into vacuum drying oven at 120 DEG C of constant temperature drying 12h.In the glove box being full of argon gas, carry out the assembling of CR2032 type button cell, use the LiPF6(EC:DMC:EMC=1:1:1 of porous polypropylene barrier film and 1mol/L) electrolyte.Every electrochemical property test is carried out again after battery standing 24h being guaranteed electrolyte complete wetting barrier film and electrode after assembling.
2. cycle performance test: Land CT2001A cell tester selected by tester, CR2032 button cell is connected on tester and carries out constant current charge-discharge, charging and discharging curve, charging and discharging capacity and the coulombic efficiency of test material directly can be obtained by testing software.The unified charging and discharging currents adopted during cycle performance test, is set to 70mA/g.
Graphene coated cupric oxide composite material in embodiment 1, electric discharge and charge specific capacity are respectively 1072mAh/g and 748mAh/g first, and after 50 circulations, capability retention is 81.5%.

Claims (4)

1. the preparation method of a graphene coated cupric oxide composite negative pole material, in described material, Graphene presents sheet and is coated in the middle of lamella by cupric oxide, in described material, the mass percentage content of cupric oxide is 20 ~ 90%, and the mass percentage content of Graphene is 10 ~ 80%; It is characterized in that: the preparation method of described material is as follows: the graphene oxide solution be first copper salt solution and the concentration of 0.02 ~ 0.2mol/L by concentration being 0.05 ~ 1mol/L mixes constant temperature and stirs 15min ~ 1h, obtain mixed solution, the mass ratio of described copper salt solution and graphene oxide solution is 1:2 ~ 2:1; Then be place 2 ~ 24h after the sodium hydroxide solution Keep agitation 0.5 ~ 2h of 0.1 ~ 0.2mol/L to mixed solution and dripping concentration, the mass percent that the dripping quantity of described sodium hydroxide solution accounts for mixed solution is 20 ~ 30%; Carry out centrifugal and hydro-thermal subsequently, the product obtained dries 12h at 120 DEG C, obtains graphene coated cupric oxide composite negative pole material; Described hydro-thermal adopts microwave radiation technology hydro-thermal, and hydrothermal temperature is 160 ~ 220 DEG C, and the hydro-thermal time is 15min ~ 2h.
2. preparation method according to claim 1, is characterized in that: described mantoquita is copper chloride, copper nitrate, copper sulphate or Schweinfurt green.
3. preparation method according to claim 1, is characterized in that: described sodium hydroxide solution adopts potassium hydroxide or ammoniacal liquor to replace.
4. preparation method according to claim 1, is characterized in that: described constant temperature stirs and adopts water bath with thermostatic control mode, and bath temperature is 20 ~ 80 DEG C.
CN201210426228.8A 2012-10-30 2012-10-30 Graphene-coated copper oxide composite cathode material and method for manufacturing same Active CN102916195B (en)

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CN103474257A (en) * 2013-09-16 2013-12-25 哈尔滨工程大学 Preparation method for graphene oxide load cupric oxide lithium ion capacitor electrode materials
CN106450466A (en) * 2016-08-31 2017-02-22 襄阳艾克特电池科技股份有限公司 Preparation technology of lithium copper oxide battery
CN108264041B (en) * 2016-12-31 2019-12-24 哈尔滨工业大学 Graphene oxide/copper oxide composite powder, preparation method thereof and preparation method of graphene/copper composite material with micro-layered structure
CN107202822B (en) * 2017-05-25 2019-04-19 济南大学 The preparation of nano silver/carbon nano tube modified electrode aurantiin molecular engram sensor
CN108199078B (en) * 2018-01-03 2019-08-30 深圳锂硫科技有限公司 A kind of lithium ion battery
CN108832114B (en) * 2018-07-09 2020-07-28 淮北师范大学 Preparation method of graphene-coated CuFeO2 composite negative electrode material
CN109626361A (en) * 2018-11-09 2019-04-16 清华大学深圳研究生院 Stablize its sodium-ion battery of high-specific surface area carbon negative pole material and preparation method and application of component modification

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