CN107732172A - A kind of lithium ion battery negative material and preparation method thereof - Google Patents

A kind of lithium ion battery negative material and preparation method thereof Download PDF

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CN107732172A
CN107732172A CN201710873664.2A CN201710873664A CN107732172A CN 107732172 A CN107732172 A CN 107732172A CN 201710873664 A CN201710873664 A CN 201710873664A CN 107732172 A CN107732172 A CN 107732172A
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lithium ion
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CN107732172B (en
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严微微
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China Jiliang University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of lithium ion battery negative material and preparation method thereof, belong to technical field of lithium ion.Its preparation technology flow is with copper sulphate（CuSO4）, trisodium citrate and polyvinylpyrrolidone, sodium hydroxide and ascorbic acid are raw material, first prepare Cu2O nanocubes, then by isopropyl titanate Hydrolyze method in Cu2O Surface coating nano-TiOs2, obtain nano-TiO2Coat Cu2O nanocube materials.The synthesis technique of material of the present invention is simple, and reaction condition is gentle, environmentally safe, and cost is relatively low, can largely produce.The nano-TiO of the present invention2Coat Cu2O nanocubes have the cyclical stability and charge-discharge performance significantly improved as lithium ion battery negative material, are adapted to the commercial application of lithium ion battery.

Description

A kind of lithium ion battery negative material and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, more particularly to a kind of lithium ion battery negative material and its preparation side Method.
Background technology
Lithium ion battery has operating voltage height, specific capacity height, memory-less effect, advantages of environment protection, extensively should For the portable electric appts such as mobile phone, notebook computer, miniature camera and electric automobile, electric bicycle, electronic The large scale electronic equipments such as instrument.Intelligent electronic device development in recent years is swift and violent, proposes requirements at the higher level to power supply, there is an urgent need to electricity Source has high energy density and power density, long cycle life, and good performance.Current commodity lithium ion Battery can not fully meet the market demand, and the electrochemistry of lithium ion battery is improved by developing high-performance electrode and electrode material Performance, promote lithium ion battery further to develop, just turn into highly important work.
The negative material of commodity lithium ion battery is mainly graphitized carbon sill at present.The very high carbon materials of degree of graphitization Material, surface anisotropy is larger, and the passivating film formed during initial charge is loose porous, it is impossible to effectively stops solvation lithium ion It is embedded altogether, the collapse of graphite linings can be caused.In addition, diffusion velocity of the lithium ion along graphite microcrystal ab axial planes is bigger than c-axis direction Much, and the insertion of lithium is carried out on graphite linings border, this causes lithium ion to spread wherein in the presence of very big dynamics to hinder Hinder, it is impossible to carry out fast charging and discharging.Therefore the research and development of high performance lithium ionic cell cathode material is by various countries researcher Extensive attention.
From J. M. Tarascon in 2000 reported first on Nature nano transition metal oxides as lithium from After the excellent properties of sub- cell negative electrode material, 3d transition metal oxides（MxOy, M=Mn, Fe, Co, Ni, Cu）Just turn into lithium The important candidate of cell negative electrode material.In above-mentioned negative material, CuO theoretical capacity is 674 mAh g-1, it is commercial carbon 2 times or so of negative material, Cu2O theoretical capacity is 372 mAh g-1.But CuO and Cu2O density is the three of carbon-based material Times or so, so as to store up lithium density, and Cu oxide with bigger volume（CuO、Cu2O or both mixture）Nontoxic nothing Evil, be readily synthesized, easily storage, thus it is as the great development potentiality of lithium ion battery negative material and application prospect, just by To higher and higher attention.
To the oxide of copper（Cuprous oxide, cupric oxide）For, cyclical stability deficiency is to influence it in lithium battery applications One of subject matter.Reason is for they（Also other transition metal oxides are included）After being reacted with lithium, it may occur that larger body Product expansion, produces serious internal stress, makes active material gradual efflorescence in cyclic process, and not only losing electricity with collector etc. connects Touch, also nano transition metal particle can be made to agglomerate into bulky grain and lose electro-chemical activity.Therefore, Cu oxide is improved （CuO、Cu2O）Cyclical stability just turn into and promote the key further applied of the material.Conventional method mainly has nanometer Change, be compound and prepare membrane electrode etc..
Publication No. CN102394305B Chinese patent literature discloses a kind of foam copper oxide/copper lithium ion battery Negative pole and preparation method thereof, the mainly Cu oxide in collector foam copper surface in situ growth stratiform, by growth in situ, Nanostructured improves the lithium battery performance of Cu oxide with membrane structure, but this material structure does not solve discharge and recharge The problem of Cu oxide volumetric expansion is with contraction and internal stress in reaction, it is limited to the improvement result of cyclical stability.
The content of the invention
The purpose of the present invention is to improve Cu2O is electrical as the cyclical stability of lithium ion battery negative material and charge and discharge Can, and propose a kind of lithium ion battery negative material and preparation method thereof.
Lithium ion battery negative material of the present invention is nano-TiO2Coat Cu2O nanocubes, Cu2O is in nanometer Cube structure, size 10-500 nm, in one layer of amorphous state TiO of its Surface coating2, TiO2Thickness 10-100 nm.
Nano-TiO of the present invention2Coat Cu2The preparation method of O nano cubic composite materials, its step are as follows：
By copper sulphate（CuSO4）, trisodium citrate and polyvinylpyrrolidone（PVP）Successively dissolve in deionized water, stir shape Into homogeneous aqueous solution, CuSO4Concentration 0.1-5 g L-1, trisodium citrate concentration 0.1-3 g L-1, PVP concentration 1-40 g L-1。 Under agitation, the NaOH aqueous solution is added dropwise（The g L of concentration 70-100-1）, after reacting 30 min, continue to be added dropwise anti-bad Hematic acid solution（Concentration 50-150 g L-1）, stirring reaction 5-30 min, stop stirring, stand 5-20 h, will production after centrifugation Thing is washed repeatedly with deionized water and absolute ethyl alcohol, is stored in absolute ethyl alcohol.
Take Cu2O ethanol solution（The g L of concentration 2-1）, deionized water is added, is stirred, is then slowly added dropwise Enter isopropyl titanate, stirring reaction 2-5 h, wash product repeatedly with deionized water and absolute ethyl alcohol after centrifugation, 70 DEG C Vacuum drying, obtains nano-TiO2Coat Cu2O nano cubic composite materials.
Negative electrode of lithium ion battery is prepared using the negative material of the present invention：Mass ratio is weighed respectively as 8:1:1 nanometer TiO2Coat Cu2O nano cubics composite material, acetylene black conductor, Kynoar（PVDF）Binding agent, PVDF is dissolved in Appropriate 1-Methyl-2-Pyrrolidone（NMP）In, stirring is until be completely dissolved, then will grind uniform reactive powder and acetylene Black conductive agent is added in above-mentioned solution, continues stirring to ensure that slurry is well mixed.Then slurry is coated uniformly on disc-shaped Foamed nickel current collector on（A diameter of 12 mm）, 80 °C of drying in vacuum drying oven are placed in, finally with 10 MPa's on tablet press machine Pressure flattens, that is, electrode slice is made.
The GND of preparation and lithium piece, barrier film are formed into CR2025 coin shape lithiums in the glove box full of high-purity argon gas Ion battery.Electrolyte is 1 mol L-1 LiPF6EC/DMC electrolyte.Lithium ion is tested using new prestige battery test system The charge-discharge performance and cyclical stability of battery.The present invention calculates TiO2Coat Cu2The specific capacity of O materials is to include TiO2With Cu2O gross mass.
Compared with prior art, the present invention has advantages below：
（1）Cu2O nanocube small volumes, absolute volume change is small in discharge and recharge reaction, can reduce material internal stress, right Improving cyclical stability has positive role.
（2）Nanometer Cu2O sizes are small, and specific surface area is big, and more positions can be provided for electrochemical reaction, are advantageous to reduce Sheet resistance and charge transfer resistance, so as to improve the activity of electrochemical reaction, high capacity and high rate performance are obtained, that is, is improved Cu2O lithium battery performance.
（3）With carbon material and Cu2O is compared, nano-TiO2There is a safer operating voltage range, body in charge and discharge process Product expansion is very small, and Stability Analysis of Structures, cyclical stability is excellent, by nano-TiO2It is coated to Cu2O nano cubic surfaces, can be effective Resist Cu2Volumetric expansions and contraction of the O in discharge and recharge reaction, the structural stability of material is remarkably improved, and then improves and follow Ring stability.
（4）TiO2Theoretical capacity close to Cu2O, therefore TiO2Cladding will not reduce the overall specific capacity of composite, This is the advantages of other materials such as carbon coated do not have.
（5）TiO of the present invention2Cladding use isopropyl titanate Hydrolyze method, this cause generation TiO2It is amorphous small crystalline substance , the loose structure being connected with each other between crystal grain be present, these architectural features can make TiO2Material has preferably circulation steady Energy storage characteristic qualitative and close to theoretical capacity, and to the infiltration inhibition very little of electrolyte and lithium ion, do not influence interior Portion Cu2O electrochemical reaction.
（6）The materials synthesis technique of the present invention is simple, and reaction condition is gentle, environmentally safe, and cost is relatively low, Ke Yi great Amount production, has larger commercial application prospect.
Brief description of the drawings
Fig. 1 is nano-TiO prepared by embodiment 12Coat Cu2The SEM photograph of O nanocubes.
Fig. 2 is nano-TiO prepared by embodiment 12Coat Cu2TEM photo of the O nanocubes after watery hydrochloric acid is handled.
Fig. 3 is nano-TiO prepared by embodiment 12Coat Cu2The cycle charge discharge electrical property of O nanocubes.
Fig. 4 is nano-TiO prepared by embodiment 22Coat Cu2The cycle charge discharge electrical property of O nanocubes.
Fig. 5 is nano-TiO prepared by embodiment 32Coat Cu2The cycle charge discharge electrical property of O nanocubes.
Embodiment
The invention will be further described with reference to embodiments.
Embodiment 1
By copper sulphate（CuSO4）, trisodium citrate and polyvinylpyrrolidone（PVP）Successively dissolve in deionized water, stir shape Into homogeneous aqueous solution, CuSO4The g L of concentration 0.19-1, the g L of trisodium citrate concentration 0.6-1, the g L of PVP concentration 20-1.Take 150 ML solution, under agitation, the NaOH aqueous solution is added dropwise（The g L of concentration 40-1）20 mL, after reacting 30 min, it is added dropwise anti- The bad mL of hematic acid solution 10（The g L of concentration 105-1）, the min of stirring reaction 15, stop stirring, stand 10 h, will production after centrifugation Thing is washed repeatedly with deionized water and absolute ethyl alcohol, is stored in absolute ethyl alcohol.
Take Cu2The O mL of ethanol solution 50（The g L of concentration 2-1）, deionized water is added, is stirred, then dropwise 0.1 mL isopropyl titanates are slowly added to, the h of stirring reaction 3, are washed product with deionized water and absolute ethyl alcohol after centrifugation Repeatedly, 70 DEG C of vacuum drying, obtain nano-TiO2Coat Cu2O nano cubic composite materials.
Fig. 1 is TiO2Coat Cu2The SEM photograph of O nanocubes, cubical structure is fairly obvious, the length of side about 200 Nm, cube face is relatively rough, and display surface is attached to layer of substance., will for the ease of observing the structure of surface cover Cu inside composite diluted hydrochloric acid dissolution2Tem observation is carried out after O, as a result as shown in Figure 2, it can be seen that a TiO2It is square Box, square box inside dimension about 200 nm, TiO2Thickness about 30-40 nm.TiO2It is made up of, presents some tiny particles The crystalline material that the methods of amorphous state feature, having higher activity, being different from hydro-thermal method synthesizes.
Negative electrode of lithium ion battery is prepared using the negative material of the present invention：Mass ratio is weighed respectively as 8:1:1 nanometer TiO2Coat Cu2O nano cubics composite material, acetylene black conductor, Kynoar（PVDF）Binding agent, PVDF is dissolved in Appropriate 1-Methyl-2-Pyrrolidone（NMP）In, stirring is until be completely dissolved, then will grind uniform reactive powder and acetylene Black conductive agent is added in above-mentioned solution, continues stirring to ensure that slurry is well mixed.Then slurry is coated uniformly on disc-shaped Foamed nickel current collector on（A diameter of 12 mm）, 80 °C of drying in vacuum drying oven are placed in, finally with 10 MPa's on tablet press machine Pressure flattens, that is, electrode slice is made.
By the negative pole and metal lithium sheet of preparation in the glove box full of high-purity argon gas（Positive pole）, barrier film composition CR2025 knobs Button-type lithium ion battery.Electrolyte is 1 mol L-1 LiPF6EC/DMC electrolyte.Tested using new prestige battery test system The charge-discharge performance and cyclical stability of lithium ion battery.Charging and discharging currents 0.1C multiplying powers, charging/discharging voltage scope 0.01-3.0 V.The specific capacity for the covering material that the present invention is calculated is to include TiO2With Cu2O gross mass.Do not coat TiO2Cu2O Nanocube also makes negative pole using same process and is assembled into lithium ion battery, and performance test is carried out using the same terms, with As comparing.
Fig. 3 is TiO prepared by embodiment one2Coat Cu2O nanocubes and pure Cu2The cycle performance of O nanocubes Comparison diagram.The TiO since circulating the 2nd2Coat Cu2O discharge capacity is sufficiently stable, maintains essentially in 370 mAh g-1, extremely 50th cyclic discharge capacity is 364 mAh g-1, and pure Cu2O cubes are recycled to the 20th cyclic discharge capacity from the 2nd 42.4% is reduced, slowly declines afterwards, is 192 mAh g to the 50th circulation-1, TiO2Cladding is to improving Cu2O circulation is steady Qualitative effect is notable.50 circulation TiO2Coat Cu2O average discharge capacity is 380 mAh g-1, and pure Cu2O is 250 mAh g-1, TiO2Cladding improves Cu2O average discharge capacity 52%, display cladding TiO2Cu can be improved2O charge-discharge performance.Circulation Charge-discharge test result shows to coat TiO2Cu can be significantly improved2O cycle performance and charge-discharge performance, TiO2Coat Cu2O receives Meter Li Fang composite materials have important application value in field of lithium ion battery.
Embodiment 2
By copper sulphate（CuSO4）, trisodium citrate and polyvinylpyrrolidone（PVP）Successively dissolve in deionized water, stir shape Into homogeneous aqueous solution, CuSO4Concentration 0.38g L-1, the g L of trisodium citrate concentration 1.2-1, the g L of PVP concentration 30-1.Take 150 ML solution, under agitation, the NaOH aqueous solution is added dropwise（The g L of concentration 40-1）40 mL, after reacting 30 min, it is added dropwise anti- The bad mL of hematic acid solution 20（The g L of concentration 105-1）, the min of stirring reaction 30, stop stirring, stand 15 h, will production after centrifugation Thing is washed repeatedly with deionized water and absolute ethyl alcohol, is stored in absolute ethyl alcohol.
Take Cu2The O mL of ethanol solution 50（The g L of concentration 2-1）, deionized water is added, is stirred, then dropwise 0.2 mL isopropyl titanates are slowly added to, the h of stirring reaction 3, are washed product with deionized water and absolute ethyl alcohol after centrifugation Repeatedly, 70 DEG C of vacuum drying, obtain nano-TiO2Coat Cu2O nano cubic composite materials.
Cu in composite2O remains in that cubical structure, the nm of the cube length of side about 350, coats TiO2Layer is in non- Crystalline state little crystal grain accumulates shell structurre, thickness 60-70 nm.
Negative electrode of lithium ion battery is made using technique same as Example 1, lithium ion battery is assembled into, is set with identical Standby and condition（0.2C multiplying powers, 0.01-3.0V voltage ranges）Cycle charge discharge electrical testing is carried out, as a result as shown in figure 4, cycle charge discharge Electrical test results show to coat TiO2Cu can be significantly improved2O cycle performance and charge-discharge performance.
Embodiment 3
By copper sulphate（CuSO4）, trisodium citrate and polyvinylpyrrolidone（PVP）Successively dissolve in deionized water, stir shape Into homogeneous aqueous solution, CuSO4Concentration 0.76g L-1, the g L of trisodium citrate concentration 2.4-1, the g L of PVP concentration 30-1.Take 150 ML solution, under agitation, the NaOH aqueous solution is added dropwise（The g L of concentration 40-1）80 mL, after reacting 30 min, it is added dropwise anti- The bad mL of hematic acid solution 40（The g L of concentration 105-1）, the min of stirring reaction 30, stop stirring, stand 15 h, will production after centrifugation Thing is washed repeatedly with deionized water and absolute ethyl alcohol, is stored in absolute ethyl alcohol.
Take Cu2The O mL of ethanol solution 50（The g L of concentration 2-1）, deionized water is added, is stirred, then dropwise 0.2 mL isopropyl titanates are slowly added to, the h of stirring reaction 3, are washed product with deionized water and absolute ethyl alcohol after centrifugation Repeatedly, 70 DEG C of vacuum drying, obtain nano-TiO2Coat Cu2O nano cubic composite materials.
Cu in composite2O remains in that cubical structure, the nm of the cube length of side about 540, coats TiO2Layer is in non- Crystalline state little crystal grain accumulates shell structurre, thickness 80-90 nm.
Negative electrode of lithium ion battery is made using technique same as Example 1, lithium ion battery is assembled into, is set with identical Standby and condition（0.2C multiplying powers, 0.01-3.0V voltage ranges）Cycle charge discharge electrical testing is carried out, as a result as shown in figure 5, cycle charge discharge Electrical test results show to coat TiO2Cu can be significantly improved2O cycle performance and charge-discharge performance.

Claims (2)

1. a kind of lithium ion battery negative material, its structure is nano-TiO2Coat Cu2O nanocubes, it is characterised in that： Cu2O is in nanocube structure, size 10-500 nm, in one layer of amorphous state TiO of its Surface coating2, TiO2Thickness 10-100 nm。
2. prepare the method for the lithium ion battery negative material described in claim 1, it is characterised in that this method includes following step Suddenly：
Copper sulphate, trisodium citrate and polyvinylpyrrolidone successively to be dissolved in deionized water, stirring forms homogeneous aqueous solution, Concentration of copper sulfate is 0.1-5 g L-1, trisodium citrate concentration is 0.1-3 g L-1, PVP concentration is 1-40 g L-1；Stirring Under the conditions of, it is 70-100 g L that concentration, which is added dropwise,-1The NaOH aqueous solution, react 30 min after, continue be added dropwise concentration be 50- 150 g L-1Ascorbic acid solution, stirring reaction 5-30 min, stop stirring, stand 5-20 h, by product after centrifugation Washed repeatedly, be stored in absolute ethyl alcohol with deionized water and absolute ethyl alcohol；
It is 2 g L to take concentration-1Cu2O ethanol solution, deionized water is added, stirs, is then slowly added to dropwise Isopropyl titanate, stirring reaction 2-5 h, product is washed repeatedly with deionized water and absolute ethyl alcohol after centrifugation, 70 DEG C true Sky is dried, and obtains nano-TiO2Coat Cu2O nano cubic composite materials.
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CN110148715A (en) * 2019-04-17 2019-08-20 湖北锂诺新能源科技有限公司 The preparation method of the rich lithium material of oxide coated by zinc
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CN110148715A (en) * 2019-04-17 2019-08-20 湖北锂诺新能源科技有限公司 The preparation method of the rich lithium material of oxide coated by zinc
CN110562955A (en) * 2019-08-06 2019-12-13 河北大学 Reed-based carbon dots, CDs-Cu2O/CuO composite material and preparation method thereof
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WO2021103934A1 (en) * 2019-11-29 2021-06-03 宁德时代新能源科技股份有限公司 Composite material having core-shell structure for battery, secondary battery, battery module, battery pack and apparatus
US11923536B2 (en) 2019-11-29 2024-03-05 Contemporary Amperex Technology Co., Limited Composite material with core-shell structure for battery, secondary battery, battery module, battery pack and apparatus
CN112479254A (en) * 2020-12-28 2021-03-12 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of three-dimensional hollow flower-shaped titanium dioxide nano material, product and application
CN113140719A (en) * 2021-04-16 2021-07-20 中科院过程工程研究所南京绿色制造产业创新研究院 Negative electrode material, preparation method thereof and lithium ion battery
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