CN102916195A - 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 PDFInfo
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- CN102916195A CN102916195A CN2012104262288A CN201210426228A CN102916195A CN 102916195 A CN102916195 A CN 102916195A CN 2012104262288 A CN2012104262288 A CN 2012104262288A CN 201210426228 A CN201210426228 A CN 201210426228A CN 102916195 A CN102916195 A CN 102916195A
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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
Technical field
The invention belongs to the 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 of lithium ion battery also more and more obtains paying attention to application.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 power fields such as electric automobile.But the limited especially specific capacity of present commercial graphite cathode performance is on the low side, make lithium ion battery realize real large-scale application in the electric automobile field, also must improve energy density, high rate during charging-discharging and the cycle life of battery cathode.
Cupric oxide is a kind of very potential lithium ion battery negative material, and theoretical capacity is 670mAhg
-1, near the twice of commercial graphite negative pole, and environmental pollution is little, with low cost.The shortcoming first of cupric oxide is low as the p-type conductivity semiconductor, and electro-chemical activity is poor; It two is to have about 174% change in volume in charge and discharge process, makes the gradually efflorescence of cupric oxide active material, loses between active material to electrically contact to cause capacity to be decayed rapidly.Cupric oxide nano and Composite are two kinds of methods of improving material property, and wherein for example carbon nano-tube is compound with material with carbon element, and composite material shows 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, it is simple to have synthetic method, the graphene coated cupric oxide composite negative pole material performance of preparation is good, has solved in the poor and charge and discharge process of cupric oxide electrode conductivuty the technical problem that gradually efflorescence causes volume lowering.
To achieve these goals, the present invention adopts following technical scheme:
A kind of graphene coated cupric oxide composite negative pole material, the mass percentage content of cupric oxide is 20～90% in the described material, the mass percentage content of Graphene is 10～80%.
Graphene presents sheet and cupric oxide is coated in the middle of the lamella in the described material.
The preparation method of graphene coated cupric oxide composite negative pole material described above, at first be that the copper salt solution of 0.02～0.2mol/L and graphene oxide solution that concentration is 0.05～1mol/L mix constant temperature and stirs 15min～1h with concentration, obtain mixed solution, the mass ratio of described copper salt solution and graphene oxide solution is 1: 2～2: 1; Then be to place 2～24h after the sodium hydroxide solution of 0.1～0.2mol/L continue to stir 0.5～2h 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 subsequently centrifugal and hydro-thermal, the product that obtains obtains graphene coated cupric oxide composite negative pole material at 120 ℃ of lower oven dry 12h.
Described mantoquita is copper chloride, copper nitrate, copper sulphate or Schweinfurt green.
Described sodium hydroxide solution can be with potassium hydroxide or aqueous ammonia to replace.
Described lasting constant temperature stirs and adopts the water bath with thermostatic control mode, and bath temperature is 20～80 ℃.
Described hydro-thermal adopts using microwave assisted aqueous extraction heat, and hydrothermal temperature is 160～220 ℃, 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 the graphene coated cupric oxide composite negative pole material, cupric oxide has effectively stoped the reunion of Graphene, the three-dimensional conductive network of Graphene formation has been accelerated the migration of electronics simultaneously, and shrink for the volumetric expansion of cupric oxide and to have reserved enough spaces, effectively alleviated the efflorescence of cupric oxide, the relative one-component of composite material chemical property has had remarkable lifting.It is simple to have synthetic method, the graphene coated cupric oxide composite negative pole material performance of preparation is good, has solved in the poor and charge and discharge process of cupric oxide electrode conductivuty the technical problem that gradually efflorescence causes volume lowering.
Description of drawings
Fig. 1 is the XRD collection of illustrative plates of the composite material that makes of example 1 of the present invention.
Fig. 2 is the SEM picture of the composite material that makes of example 1 of the present invention.
Embodiment
The present invention is described further below in conjunction with the drawings and specific embodiments.
Embodiment one
Take by weighing 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, with 100ml concentration be that (concentration of graphene oxide solution is demarcated in advance for the graphene oxide solution of 0.17mol/L, the Graphene quality is about half of graphene oxide quality in the solution) mix and stir 30min, keep water bath with thermostatic control, Temperature Setting is 50 ℃, and dripping concentration is the lasting constant temperature stirring of the sodium hydroxide solution 120ml 1h of 0.2mol/L; Centrifugal behind the placement 8h, adopt subsequently using microwave assisted aqueous extraction heat, hydrothermal temperature is 180 ℃, the hydro-thermal time is 1h; Last 120 ℃ of oven dry 12h obtain graphene coated cupric oxide composite negative pole material.
The mass percentage content of cupric oxide is 80% in the graphene coated cupric oxide composite negative pole material that present embodiment obtains, and the mass percentage content of Graphene is 20%.The XRD collection of illustrative plates of the composite material that makes and SEM picture are as depicted in figs. 1 and 2.
Embodiment two
Take by weighing 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, with 100ml concentration be that the graphene oxide solution of 0.083mol/L mixes and stirs 15min, keep water bath with thermostatic control, Temperature Setting is 30 ℃, and dripping concentration is the lasting constant temperature stirring of the sodium hydroxide solution 140ml 2h of 0.2mol/L; Centrifugal behind the placement 4h, adopt subsequently using microwave assisted aqueous extraction heat, hydrothermal temperature is 160 ℃, the hydro-thermal time is 30min; Last 120 ℃ of oven dry 12h obtain graphene coated cupric oxide composite negative pole material.
The mass percentage content of cupric oxide is 90% in the graphene coated cupric oxide composite negative pole material that present embodiment obtains, and the mass percentage content of Graphene is 10%.
Embodiment three
Take by weighing 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, with 100ml concentration be that the graphene oxide solution of 0.333mol/L mixes and stirs 1h, keep water bath with thermostatic control, Temperature Setting is 60 ℃, and dripping concentration is the lasting constant temperature stirring of the potassium hydroxide solution 90ml 1.5h of 0.2mol/L; Centrifugal behind the placement 12h, adopt subsequently using microwave assisted aqueous extraction heat, hydrothermal temperature is 200 ℃, the hydro-thermal time is 2h.Last 120 ℃ of oven dry 12h obtain graphene coated cupric oxide composite negative pole material.
The mass percentage content of cupric oxide is 60% in the graphene coated cupric oxide composite negative pole material that present embodiment obtains, and the mass percentage content of Graphene is 40%.
Embodiment four
Take by weighing 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, with 100ml concentration be that the graphene oxide solution of 0.667mol/L mixes and stirs 45min, keep water bath with thermostatic control, Temperature Setting is 80 ℃, and dripping concentration is that 30% ammonia spirit 20ml continues constant temperature stirring 30min; Centrifugal behind the placement 24h, adopt subsequently using microwave assisted aqueous extraction heat, hydrothermal temperature is 220 ℃, the hydro-thermal time is 1.5h.Last 120 ℃ of oven dry 12h obtain graphene coated cupric oxide composite negative pole material.
The mass percentage content of cupric oxide is 20% in the graphene coated cupric oxide composite negative pole material that present embodiment obtains, 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 and fully grind the furnishing thickener in the 1-METHYLPYRROLIDONE (NMP), with scraper it evenly is coated on the Copper Foil.After 80 ℃ of rough oven dry the Copper Foil stamping-out being become diameter is the disk of 10mm, uses roll squeezer with the diaphragm compacting, continues to put into vacuum drying oven at 120 ℃ of constant temperature drying 12h.In being full of the glove box 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.Assemble and battery standing 24h is guaranteed to carry out every electrochemical property test behind electrolyte complete wetting barrier film and the electrode after complete again.
2. cycle performance test: tester is selected Land CT2001A cell tester, the CR2032 button cell is connected to carries out constant current charge-discharge on the tester, can directly obtain by testing software the charging and discharging curve of test material, charging and discharging capacity and enclosed pasture efficient.The unified charging and discharging currents that adopts during the cycle performance test is set to 70mA/g.
Graphene coated cupric oxide composite material among the embodiment 1, discharge and charge ratio capacity are respectively 1072mAh/g and 748mAh/g first, and capability retention is 81.5% after 50 circulations.
Claims (7)
1. graphene coated cupric oxide composite negative pole material, it is characterized in that: the mass percentage content of cupric oxide is 20～90% in the described material, the mass percentage content of Graphene is 10～80%.
2. graphene coated cupric oxide composite negative pole material according to claim 1 is characterized in that: Graphene presents sheet and cupric oxide is coated in the middle of the lamella in the described material.
3. the preparation method of claim 1 or 2 described graphene coated cupric oxide composite negative pole materials, it is characterized in that: at first be that the copper salt solution of 0.02～0.2mol/L and graphene oxide solution that concentration is 0.05～1mol/L mix constant temperature and stirs 15min～1h with concentration, obtain mixed solution, the mass ratio of described copper salt solution and graphene oxide solution is 1: 2～2: 1; Then be to place 2～24h after the sodium hydroxide solution of 0.1～0.2mol/L continue to stir 0.5～2h 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 subsequently centrifugal and hydro-thermal, the product that obtains obtains graphene coated cupric oxide composite negative pole material at 120 ℃ of lower oven dry 12h.
4. preparation method according to claim 3, it is characterized in that: described mantoquita is copper chloride, copper nitrate, copper sulphate or Schweinfurt green.
5. preparation method according to claim 3 is characterized in that: described sodium hydroxide solution can be with potassium hydroxide or aqueous ammonia to replace.
6. preparation method according to claim 3 is characterized in that: described constant temperature stirs and adopts the water bath with thermostatic control mode, and bath temperature is 20～80 ℃.
7. preparation method according to claim 3 is characterized in that: described hydro-thermal adopts using microwave assisted aqueous extraction heat, and hydrothermal temperature is 160～220 ℃, and the hydro-thermal time is 15min～2h.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107202822A (en) * | 2017-05-25 | 2017-09-26 | 济南大学 | The preparation of Nano Silver/carbon nano tube modified electrode aurantiin molecular engram sensor |
| CN108199078A (en) * | 2018-01-03 | 2018-06-22 | 深圳锂硫科技有限公司 | A kind of lithium ion battery |
| CN108264041A (en) * | 2016-12-31 | 2018-07-10 | 哈尔滨工业大学 | Graphene oxide/copper oxide composite powder and preparation method thereof, microcosmic stratiform structure graphite alkene/method of manufacturing carbon/carbon-copper composite material |
| CN108832114A (en) * | 2018-07-09 | 2018-11-16 | 淮北师范大学 | A kind of preparation method of graphene coated CuFeO2 composite negative pole 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 |
| CN112723500A (en) * | 2019-10-28 | 2021-04-30 | 华东理工大学 | Environment-friendly efficient nano copper ion compound and preparation method and application thereof |
| CN113457619A (en) * | 2021-05-10 | 2021-10-01 | 沈阳大学 | Three-dimensional CuxO graphene and preparation method and application thereof |
| CN113675393A (en) * | 2021-08-20 | 2021-11-19 | 西安热工研究院有限公司 | Morphology-controllable high-performance lithium ion battery negative electrode material and preparation method thereof |
| CN114566635A (en) * | 2022-03-08 | 2022-05-31 | 南京大学 | Composite electrode material, preparation method thereof and potassium ion battery |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108264041A (en) * | 2016-12-31 | 2018-07-10 | 哈尔滨工业大学 | Graphene oxide/copper oxide composite powder and preparation method thereof, microcosmic stratiform structure graphite alkene/method of manufacturing carbon/carbon-copper composite material |
| 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 |
| CN107202822A (en) * | 2017-05-25 | 2017-09-26 | 济南大学 | The preparation of Nano Silver/carbon nano tube modified electrode aurantiin molecular engram sensor |
| CN108199078A (en) * | 2018-01-03 | 2018-06-22 | 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 |
| CN108832114A (en) * | 2018-07-09 | 2018-11-16 | 淮北师范大学 | A kind of preparation method of graphene coated CuFeO2 composite negative pole 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 |
| CN112723500A (en) * | 2019-10-28 | 2021-04-30 | 华东理工大学 | Environment-friendly efficient nano copper ion compound and preparation method and application thereof |
| CN112723500B (en) * | 2019-10-28 | 2023-10-27 | 华东理工大学 | Environment-friendly high-efficiency nano copper ion compound and preparation method and application thereof |
| CN113457619A (en) * | 2021-05-10 | 2021-10-01 | 沈阳大学 | Three-dimensional CuxO graphene and preparation method and application thereof |
| CN113675393A (en) * | 2021-08-20 | 2021-11-19 | 西安热工研究院有限公司 | Morphology-controllable high-performance lithium ion battery negative electrode material and preparation method thereof |
| CN114566635A (en) * | 2022-03-08 | 2022-05-31 | 南京大学 | Composite electrode material, preparation method thereof and potassium ion battery |
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