CN102637860A - CuO/Cu composite anode material used for lithium ion battery as well as preparation method and application thereof - Google Patents
CuO/Cu composite anode material used for lithium ion battery as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of energy materials, and in particular relates to preparation of a novel lithium ion battery electrode material and the storage and conversion of the electrochemical property of the novel lithium ion battery electrode material. The preparation method of the CuO/Cu composite anode material used for the lithium ion battery is characterized in that the composite anode material adopts copper oxide powder of which the particle size is 30nm-10mu m as a raw material; the raw material is reduced for 10-120 minutes under the hydrogenous reducing mixed gas atmosphere at the temperature of 50-200DEG C in an atmosphere furnace; and the content of copper in the composite material accounts for 0.5-40wt.% of the composite material. The preparation method of the CuO/Cu composite lithium-ion anode material has the advantages of abundant raw material resource, low cost, simple preparation equipment and high yield and is suitable for scale production.
Description
Technical field
The invention belongs to field of energy source materials.Be specifically related to the preparation of new type lithium ion battery electrode material and the storage and the conversion of electrochemical energy thereof.
Technical background
Along with modern society to energy demand increase day by day and to the pay attention to day by day of environmental protection requirement; The limited reserves of tradition fossil energy increasingly sharpen with the contradiction of its environmental pollution and development of modern society; Lithium ion battery is as the green secondary power supply that grows up over a kind of nearly 20 years; Because its energy density is high, have extended cycle life, self discharge is little, memory-less effect, advantages of environment protection, in the power supply of small portable movable electrical appliances such as notebook computer, mobile phone, is used widely.The deposit of electric automobile, hybrid-electric car, electric bicycle, solar energy and wind energy and conversion at present, electric tool increase the increasing demand of the secondary power supply of the high-energy-density of safety, environmental protection and high power density, and wherein lithium ion battery has the potentiality that satisfy its application requirements.The positive electrode of commercial Li-ion batteries is respectively LiCoO at present
2With the graphitic carbon material, its theoretical capacity score of the game is not about 140 mAh/g and 372 mAh/g, and they can't satisfy the requirement of high power density, high-energy-density on capacity.LiCoO as positive electrode
2Because it contains the Co noble metal, the cost of raw material is high, and it contains toxic side effect, existing problems also in fail safe.As the graphitic carbon of negative material, its density has only 2.2 –, 2.4 g/cm
3, this has reduced the volume of battery capacity to a great extent, and is particularly unfavorable to the bulk density of large-sized battery.Thereby in recent years no matter for positive electrode or negative material, countries in the world have all dropped into great amount of manpower and material resources are carried out extensive studies and exploitation.
Multiple 3d transition metal (comprising Ti, Fe, Cu, Co and Ni etc.) oxide has the characteristic of high power capacity as lithium ion battery negative material the time.Wherein CuO is 674 mAh/g as its theoretical capacity of lithium ion battery negative material, is more than 2 times of graphite cathode material.Its weight density is 6.32 g/cm
3, be nearly 3 times of graphite, thereby it also has the big advantage of storage lithium bulk density as lithium ion battery negative material.In addition, CuO also has easy storage and advantage such as nontoxic, thereby is a kind of lithium ion battery negative material of new generation that has development and application potential.
CuO mainly contains two big types of liquid phase method and solid phase methods mainly through the method system of chemical reaction at present.The method of liquid phase method is numerous, and if any the precipitation method, spray pyrolysis, pure hot method, sol-gal process and template etc., the whole bag of tricks differs from one another and advantage.To react raw material in the solid phase method obtains through simple chemical reaction under room temperature or heat treated condition.The different-shape of distinct methods preparation and the CuO of size show the very big chemical property of difference.
The disadvantage that CuO is used for lithium ion battery negative material is a cyclical stability difference and irreversible capacity is high first.Wherein the main cause of cyclical stability difference is that CuO has produced about 170% volumetric expansion in embedding lithium process, produces very big stress, thereby makes the efflorescence of CuO active material and lose effective contact, and the utilance of active material is constantly reduced; The main cause that irreversible capacity is big first is CuO in its reaction of embedding lithium process first:
In Li
2The O part is irreversible.Reduce CuO particle size to nanometer size, adopt one-dimensional nano structure etc., help improving the release of the stress that CuO produces owing to removal lithium embedded in cyclic process, can effectively improve the cyclical stability of CuO.CuO and other material is compound, as compound alleviating the volumetric expansion of CuO, and form Li in the compound promotion CuO of the Ni cyclic process first with the graphite of 3D structure
2The O decomposition waits the cyclical stability that also helps improving CuO.
Summary of the invention
In order to improve the cyclical stability of CuO; An object of the present invention is to provide the preparation method of the CuO/Cu composite negative pole material that a kind of lithium ion battery uses and by the composite negative pole material of this method preparation; Method condition and the technology for preparing the CuO/Cu composite material of the present invention is simple and easy to control, is fit to large-scale production.Lithium ion or the lighium polymer that another object of the present invention provides the composite negative pole material of using above-mentioned preparation once and secondary cell.
In order to realize first above-mentioned purpose, the technical scheme below the present invention has adopted:
The preparation method of the CuO/Cu composite negative pole material that a kind of lithium ion battery is used; The employing particle size of this composite negative pole material is that the cupric oxide powder of 30nm～10 μ m is raw material; Raw material in atmosphere furnace, under 50～200 ℃ temperature, are reduced in containing the hydrogen reduction mixed-gas atmosphere; Recovery time is 10～120 minutes, and the content of copper is 0.5～40wt.% of composite material percentage by weight in the composite material.
As preferably, the content of copper is 1～10wt.% of composite material percentage by weight in the above-mentioned composite material.
As preferably, above-mentioned cupric oxide powder particle size is 50nm～10 μ m.
As preferably, above-mentioned reduction temperature is 80～120 ℃.
As preferably, the above-mentioned hydrogen reduction mist that contains is hydrogen, nitrogen hydrogen or argon hydrogen mixture, and wherein the content of hydrogen is 5～50% in the mist.
In order to realize second above-mentioned purpose, the technical scheme below the present invention has adopted:
Lithium ion or lighium polymer once and secondary cell, the negative material of this battery adopts above-mentioned composite negative pole material.
The present invention reduces in reducing atmosphere through the cupric oxide powder with nanometer to micron-scale, and through the regulation and control to oxidizing temperature and time, forms one deck Cu at the CuO particle surface, forms the CuO/Cu composite material.Because the superior electrical conductivity of Cu has been improved CuO electrically contacting in cyclic process, help improving the utilance and the electronic conductivity that improves material of active material.The good toughness of Cu is alleviated the stress that CuO produces to a certain extent in the removal lithium embedded process, reduce its efflorescence.In addition, the surface coated Cu of CuO also helps the Li that promotes that CuO forms in embedding lithium process first
2The decomposition of O reduces the irreversible capacity first of electrode.Thereby the CuO/Cu composite material that the present invention obtains has good comprehensive electrochemical.The method for preparing CuO/Cu compound lithium ion multipole material of the present invention, the raw material source of employing is abundant, cost is low, and preparation equipment is simple, and productive rate is high, is fit to large-scale production.
With CuO/Cu composite material of the present invention is negative material, for electrode preparation is become button cell, shows good comprehensive electrochemical with the lithium sheet.Wherein, the content of Cu increases in the composite material, helps battery and obtains better cyclical stability, suitably reduces the specific discharge capacity that the content of Cu in the composite material helps improving electrode.
Description of drawings
Fig. 1 is the used raw-material ESEM pattern of CuO of embodiment 1 – 3.
Fig. 2 is the ESEM pattern of the CuO/Cu composite material that obtained of embodiment 2.
Fig. 3 is embodiment 1,2 and the CuO/Cu composite material of 3 acquisitions and the X-ray diffracting spectrum of used raw material CuO thereof.
Fig. 4 is that collection of illustrative plates is analyzed in the Rietveld refine of the CuO/Cu composite material X-ray diffraction that obtained of embodiment 2.
Fig. 5, Fig. 6 are respectively first three time charging and discharging curves of the CuO/Cu composite material that obtained of embodiment 1 and 2.
Fig. 7 is the CuO/Cu composite material that obtained of embodiment 3 and the cycle performance curve of initial CuO.
Embodiment
Following examples can be understood the present invention better, but the present invention is not limited to following examples.
Embodiment 1
Get the commercial CuO powder that a certain amount of particle size is about 50 nm, under 80 ℃ temperature, be incubated 30 minutes in the hydrogen then, obtain the CuO/Cu composite material.The content of Cu is analyzed through the Rietveld of X-ray diffraction refine and is about 0.5wt.% in the composite material.
This composite material is used for lithium ion battery negative material; With the lithium sheet for electrode preparation is become button cell; In measuring current is 67 mA/g, and voltage range is under the condition of 20 mV-3V, and the reversible capacity first of battery is 500 mAh/g; Compare high about 50 mAh/g of CuO original material, and improved the cyclical stability of material without reduction.
Embodiment 2
Getting a certain amount of particle size is the commercial CuO powder of 50 nm, and insulation is 30 minutes in 100 ℃ hydrogen atmosphere, obtains the CuO/Cu composite material.The content of Cu is analyzed through the Rietveld of X-ray diffraction refine and is about 5 wt.% in the composite material.
This composite material is used for lithium ion battery negative material; For electrode preparation is become button cell, is 67 mA/gs in measuring current with the lithium sheet, and voltage range is under the condition of 20 mV – 3V; The reversible capacity first of electrode reaches 515 mAh/g; And capacity further rises to 550 mAh/g after initial several cycles, than high about 100 mAh/g of CuO original material without reduction, and has improved the cyclical stability of material.
Embodiment 3
Getting a certain amount of particle size is the commercial CuO powder of 50 nm, under 120 ℃ temperature, is incubated 30 minutes in the hydrogen atmosphere then, obtains the CuO/Cu composite material.The content of Cu is analyzed through the Rietveld of X-ray diffraction refine and is about 38 wt.% in the composite material.
This composite material is used for lithium ion battery negative material; For electrode preparation is become button cell, is 67 mA/gs in measuring current with the lithium sheet, and voltage range is under the condition of 20 mV-3V; The reversible capacity first of electrode is 280 mAh/g, and composite material has excellent cyclical stability.
Embodiment 4
Getting a certain amount of particle size is the commercial CuO of about 10 μ m, in the mixed atmosphere of 30 vol% hydrogen and argon gas, reducing 60 minutes under 100 ℃ the temperature, obtains the CuO/Cu composite material then, can be used for lithium ion battery negative material.
Embodiment 5
Getting a certain amount of particle size is the commercial CuO of about 30 nm, in the mixed atmosphere of 5 vol% hydrogen and nitrogen, reducing 120 minutes under 80 ℃ the temperature, obtains the CuO/Cu composite material then.This composite material is used for lithium ion battery negative material, for electrode preparation is become button cell, is 67 mA/gs in measuring current with the lithium sheet, and voltage range is under the condition of 20 mV-3V, and material list reveals high capacity and good cycle performance.
Embodiment 6
Getting a certain amount of particle size is the commercial CuO of about 500 nm, under 120 ℃ temperature, in hydrogen atmosphere, reduces 10 minutes then, obtains the CuO/Cu composite material, can be used for lithium ion battery negative material.
Claims (7)
1. the preparation method of the CuO/Cu composite negative pole material used of a lithium ion battery; It is characterized in that: the employing particle size of this composite negative pole material is that the cupric oxide powder of 30nm～10 μ m is raw material; Raw material in atmosphere furnace, under 50～200 ℃ temperature, are reduced in containing the hydrogen reduction mixed-gas atmosphere; Recovery time is 10～120 minutes, and the content of copper is 0.5～40wt.% of composite material percentage by weight in the composite material.
2. the preparation method of the CuO/Cu composite negative pole material that a kind of lithium ion battery according to claim 1 is used is characterized in that: the content of copper is 1～10wt.% of composite material percentage by weight in the composite material.
3. the preparation method of the CuO/Cu composite negative pole material that a kind of lithium ion battery according to claim 1 is used is characterized in that: the cupric oxide powder particle size is 50nm～10 μ m.
4. the preparation method of the CuO/Cu composite negative pole material that a kind of lithium ion battery according to claim 1 is used is characterized in that: reduction temperature is 80～120 ℃.
5. the preparation method of the CuO/Cu composite negative pole material that a kind of lithium ion battery according to claim 1 is used is characterized in that: containing the hydrogen reduction mist is hydrogen, nitrogen hydrogen or argon hydrogen mixture, and wherein the content of hydrogen is 5～50% in the mist.
6. the CuO/Cu composite negative pole material that the lithium ion battery that makes according to any described preparation method of claim of claim 1 ~ 5 is used.
7. lithium ion or lighium polymer once and secondary cell is characterized in that: the negative material of this battery adopts the described composite negative pole material of claim 6.
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Cited By (2)
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|---|---|---|---|---|
| CN106531966A (en) * | 2016-12-12 | 2017-03-22 | 北京科技大学 | Preparation method for nanometer Cu@CuO material and application of nanometer Cu@CuO material to lithium ion battery |
| CN108987703A (en) * | 2018-07-17 | 2018-12-11 | 澳洋集团有限公司 | A kind of preparation method based on copper oxide composite lithium ion battery negative electrode material |
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| CN106531966B (en) * | 2016-12-12 | 2019-06-11 | 北京科技大学 | Nanometer and its is applied Cu@CuO material preparation method in lithium ion battery |
| CN108987703A (en) * | 2018-07-17 | 2018-12-11 | 澳洋集团有限公司 | A kind of preparation method based on copper oxide composite lithium ion battery negative electrode material |
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