CN103227328A - Cuprous oxide/porous carbon composite material as lithium ion battery cathode material and preparation method thereof - Google Patents
Cuprous oxide/porous carbon composite material as lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- CN103227328A CN103227328A CN2012104883090A CN201210488309A CN103227328A CN 103227328 A CN103227328 A CN 103227328A CN 2012104883090 A CN2012104883090 A CN 2012104883090A CN 201210488309 A CN201210488309 A CN 201210488309A CN 103227328 A CN103227328 A CN 103227328A
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Abstract
The invention relates to a cuprous oxide/porous carbon composite material as a lithium ion battery cathode material and a preparation method thereof, and belongs to the technical field of chemical electrode materials. The preparation method comprises the following steps of adding porous carbon into a copper sulphate solution, carrying out ultrasonic dispersion, adding sodium hydroxide and glucose into the mixed solution at a temperature of 50 to 120 DEG C for a reaction, then carrying out washing pumping filtration until the pH value of the filtrate is 7, and carrying out vacuum drying of the pumping filtration products to obtain the cuprous oxide/porous carbon composite material having a nano-porous structure. The preparation method has simple processes, is feasible, and has strong preparation parameter controllability. The cuprous oxide/porous carbon composite material can be used as a lithium ion battery cathode material and has excellent charge and discharge performances, high cycling stability and a high rate capability.
Description
Technical field
The present invention relates to a kind of cuprous oxide/porous carbon composite material and preparation method thereof, belong to chemical industry electrode material technical field as lithium ion battery negative material.
Background technology
The energy and material are the bases of physical development.In recent years, because the development that science and technology is advanced by leaps and bounds, the consumption of non-renewable resources such as oil is quickened, and energy problem has become the difficult problem of the urgent need solution that can not be ignored.Lithium ion battery have specific energy height, operating voltage height, self-discharge rate low, have extended cycle life, unique advantage such as pollution-free, be considered to can substitute one of secondary renewable resource of oil.Wherein lithium ion battery negative material is one of key factor of restriction capacity of lithium ion battery.
Cuprous oxide has active electron hole pair system as P type oxide semiconductor material, obtains at aspects such as photoelectrocatalysiss paying close attention to and extensive use.At present existing relevant report as lithium ion battery negative material, has the theoretical capacity that is higher than the conventional carbon material and certain application potential with cuprous oxide.The cuprous oxide pattern is various, and the preparation method is simple, and controllability is strong, but when the negative material because self bigger volumetric expansion effect, it is relatively poor to have cyclical stability in charge and discharge process, and especially there is the low excessively problem of enclosed pasture efficient first in the shortcoming that capacity attenuation is too fast.In addition, because its conductivity is relatively poor, high rate performance also needs further raising.Because porous carbon materials has abundant pore passage structure and good electrical conductivity, the present invention selects the complex carrier of porous carbon as cuprous oxide, in the process of the synthetic cuprous oxide of a step solwution method, make in the duct of cuprous oxide crystal at porous carbon and grow, prepare cuprous oxide/porous carbon composite negative pole material with nano-porous structure.As the carrier of carrying cuprous oxide, porous carbon has certain cushioning effect to cuprous oxide volumetric expansion in the charge and discharge process, and its good electrical conductivity also can further improve electrically contacting of combination electrode, reduces the diffusion rate of reaction impedance and raising lithium ion.Show high circulating and reversible capacity and high rate performance when therefore, cuprous oxide/porous carbon nano composite material of making of the present invention is as lithium ion battery negative material.
Summary of the invention
The objective of the invention is for solve existing lithium ion battery cuprous oxide negative material poorly conductive, capacity attenuation is fast and the unfavorable problem of high rate performance, proposes a kind of cuprous oxide as lithium ion battery negative material/porous carbon composite material and preparation method thereof.
The objective of the invention is to be achieved through the following technical solutions.
A kind of cuprous oxide as lithium ion battery negative material of the present invention/porous carbon composite material is made up of cuprous oxide and porous carbon, calculates with the gross mass of this composite material, and the quality percentage composition of each several part is:
Porous carbon 90%-10%.
The preparation method of a kind of cuprous oxide of the present invention/porous carbon composite material as lithium ion battery negative material, concrete preparation process is as follows:
1) porous carbon is joined in the copper-bath ultrasonic dispersion;
2) under temperature is 50～120 ℃ condition, in the solution that step 1) obtains, add NaOH and glucose, to react, the reaction time is 15min～12h;
3) after question response was finished, the washing suction filtration was neutral to filtrate pH, with suction filtration product vacuum drying, obtains having the cuprous oxide/porous carbon composite material of nano-porous structure.
Ultrasonic jitter time is 5～120min in the step 1).
The concentration of copper-bath is 0.01～0.5g/mL in the step 1).
The mass ratio of porous carbon and copper sulphate solute is 1 in the step 1): 0.05-10.
Step 2) NaOH that adds in and the mass ratio of copper sulphate solute are 1: 0.01-10.
Step 2) glucose that adds in and the mass ratio of copper sulphate solute are 1: 0.01-10.
Washing is with deionized water and ethanol washing in the step 4).
Beneficial effect
The present invention can be used as the matrix of carrying cuprous oxide with porous carbon, for its change in volume provides the space of a buffering, has avoided the efflorescence and the inefficacy of electrode.Therefore, in order effectively to suppress cuprous oxide serious volumetric expansion effect in charge and discharge process, itself and porous carbon are carried out compound, prepare cuprous oxide/porous carbon composite material with nanostructure.Preparation is simple, and the preparation parameter controllability is strong.The abundant pore passage structure that porous carbon has provides cushion space for the change in volume of cuprous oxide, simultaneously the conductivity of composite material also is increased, and (in current density is 100mAg to show excellent charging and discharging performance and cyclical stability as lithium ion battery negative material
-1Down, reversible capacity is 884.4mAhg after 100 weeks of circulation
-1) and high high rate performance (in current density is 1000mAg
-1Discharge and recharge under the system, reversible capacity is 600mAhg
-1).
Description of drawings
Fig. 1 is the XRD figure of cuprous oxide/porous carbon composite negative pole material.
Fig. 2 is the TEM figure of cuprous oxide/porous carbon composite negative pole material.
Fig. 3 is that cuprous oxide/porous carbon composite negative pole material is at 100mAg
-1The discharge curve in 100 weeks of charge and discharge cycles.
Fig. 4 is that cuprous oxide/porous carbon composite negative pole material is at 100mAg
-1, 200mAg
-1, 500mAg
-1And 1000mAg
-1Under specific capacity and enclosed pasture efficiency curves figure when discharging and recharging.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is elaborated
Embodiment
The preparation method of a kind of cuprous oxide/porous carbon composite material as lithium ion battery negative material, concrete preparation process is as follows:
1) 1g copper sulphate is dissolved in the 80mL deionized water, magnetic agitation is fully dissolved it;
2) in the solution that 0.8g porous carbon adding step 1) is obtained, ultrasonic dispersion 30min is well dispersed in the solution porous carbon;
3) 0.72g NaOH and 0.65g glucose being added step 2) in the solution that obtains, reaction temperature is 80 ℃, continues to stir to stop after 15 minutes stirring, ageing 60min leaves standstill and obtains sediment;
4) sediment that step 3) is obtained is neutral with deionized water wash, suction filtration to filtrate pH, with 120 ℃ of bakings of suction filtration product vacuum 4h, obtain having the cuprous oxide/porous carbon composite material of nano-porous structure, its XRD figure as shown in Figure 1, TEM schemes as shown in Figure 2;
Cuprous oxide/porous carbon the composite material of method for preparing is applied to carry out charging and discharging capacity and cycle performance test behind the lithium ion battery negative material: cuprous oxide/porous carbon materials and conductive agent Super.P, binding agent Kynoar (PVDF) mixed of 60%:20%:20% are by mass percentage made electrode slice as work electrode, lithium metal is to electrode, the LiF of 1mol/L
6/ EC-DMC (volume ratio 1: 1) is an electrolyte, is assembled into simulated battery in the argon gas atmosphere glove box.Simulated battery is carried out charge-discharge test, and voltage range is 0.01～3V (vs.Li
+/ Li), current density is 100mAg
-1, 200mAg
-1, 500mAg
-1And 1000mAg
-1
Test result: cuprous oxide/porous carbon composite negative pole material is at 100mAg
-1The discharge curve in 100 weeks of charge and discharge cycles is 100mAg in current density as shown in Figure 3
-1The time, discharge (embedding lithium) specific capacity and charging (taking off lithium) specific capacity are respectively 1382.4mAhg first
-1, 885.6mAhg
-1, enclosed pasture efficient is 64% first; Reversible capacity is 884.4mAhg after 100 weeks of circulation
-1Cuprous oxide/porous carbon composite negative pole material high rate performance and enclosed pasture efficiency curves are 200mAg in current density as shown in Figure 4
-1, 500mAg
-1And 1000mAg
-1The time, corresponding specific discharge capacity is respectively 792.2mAhg
-1, 719.2mAhg
-1And 600.8mAhg
-1
Claims (8)
1. the cuprous oxide as lithium ion battery negative material/porous carbon composite material is characterized in that: the gross mass with this composite material is calculated, and the quality percentage composition of each several part is:
Cuprous oxide 10%-90%;
Porous carbon 90%-10%.
2. the preparation method of the described composite material of claim 1 is characterized in that concrete preparation process is as follows:
1) porous carbon is joined in the copper-bath ultrasonic dispersion;
2) under temperature is 50～120 ℃ condition, in the solution that step 1) obtains, add NaOH and glucose, to react, the reaction time is 15min～12h;
3) after question response was finished, the washing suction filtration was neutral to filtrate pH, with suction filtration product vacuum drying, obtains having the cuprous oxide/porous carbon composite material of nano-porous structure.
3. preparation method according to claim 1 is characterized in that: ultrasonic jitter time is 5～120min in the step 1).
4. preparation method according to claim 1 is characterized in that: the concentration of copper-bath is 0.01～0.5g/mL in the step 1).
5. preparation method according to claim 1 is characterized in that: the mass ratio of porous carbon and copper sulphate solute is 1 in the step 1): 0.05-10.
6. preparation method according to claim 1 is characterized in that: step 2) in the NaOH that adds and the mass ratio of copper sulphate solute be 1: 0.01-10.
7. preparation method according to claim 1 is characterized in that: step 2) in the glucose that adds and the mass ratio of copper sulphate solute be 1: 0.01-10.
8. preparation method according to claim 1 is characterized in that: washing is with deionized water and ethanol washing in the step 4).
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103400975A (en) * | 2013-08-13 | 2013-11-20 | 西南大学 | Preparation method of Cu2O secondary battery anode material |
| CN104512878A (en) * | 2013-09-30 | 2015-04-15 | 上海交通大学 | Method for generating cubic nano cuprous oxide particles on surface of moulded porous carbon |
| CN105826525A (en) * | 2016-03-22 | 2016-08-03 | 太原理工大学 | Copper oxide and activated carbon composite material and preparation method and application thereof |
| CN107732172A (en) * | 2017-09-25 | 2018-02-23 | 中国计量大学 | A kind of lithium ion battery negative material and preparation method thereof |
| CN109387552A (en) * | 2018-10-12 | 2019-02-26 | 温州大学 | A kind of copper-based porous carbon microsphere composite material and preparation method and purposes |
| CN111082066A (en) * | 2019-12-25 | 2020-04-28 | 山东大学 | Three-dimensional lithium-philic conductive network material, preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580742A (en) * | 2012-02-05 | 2012-07-18 | 淮北师范大学 | Activated carbon-loaded cuprous oxide photocatalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580742A (en) * | 2012-02-05 | 2012-07-18 | 淮北师范大学 | Activated carbon-loaded cuprous oxide photocatalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ANUBHA GOYAL ET AL: "Flexible Carbon Nanotube–Cu2O Hybrid Electrodes for Li-Ion Batteries", 《SMALL》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103400975A (en) * | 2013-08-13 | 2013-11-20 | 西南大学 | Preparation method of Cu2O secondary battery anode material |
| CN103400975B (en) * | 2013-08-13 | 2015-10-14 | 西南大学 | Cu 2the preparation method of O secondary cell anode material |
| CN104512878A (en) * | 2013-09-30 | 2015-04-15 | 上海交通大学 | Method for generating cubic nano cuprous oxide particles on surface of moulded porous carbon |
| CN104512878B (en) * | 2013-09-30 | 2016-08-17 | 上海交通大学 | A kind of method at shaping porous carbon superficial growth cube nano cuprous oxide particle |
| CN105826525A (en) * | 2016-03-22 | 2016-08-03 | 太原理工大学 | Copper oxide and activated carbon composite material and preparation method and application thereof |
| CN107732172A (en) * | 2017-09-25 | 2018-02-23 | 中国计量大学 | A kind of lithium ion battery negative material and preparation method thereof |
| CN109387552A (en) * | 2018-10-12 | 2019-02-26 | 温州大学 | A kind of copper-based porous carbon microsphere composite material and preparation method and purposes |
| CN109387552B (en) * | 2018-10-12 | 2021-04-16 | 温州大学 | Copper-based porous carbon microsphere composite material and preparation method and application thereof |
| 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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Application publication date: 20130731 |