CN105742617A - Preparation method of cathode material lithium cuprate for lithium-ion battery - Google Patents
Preparation method of cathode material lithium cuprate for lithium-ion battery Download PDFInfo
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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
- H01M4/48—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
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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
- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a cathode material lithium cuprate for a lithium-ion battery. The method comprises the following steps: firstly, adding lithium hydrate to deionized water for dissolving to obtain a clear solution of the lithium hydrate; adding the solution to a nano ball-mill, then adding cuprous oxide and the deionized water, carrying out ball-milling while stirring and controlling the solid content of slurry to be 25%-35%, wherein the sizes of suspended particles in the slurry obtained after ball-milling are 270-330nm; stirring the slurry evenly and then carrying out spray drying; and placing the obtained precursor powder into an electric furnace at 650-700 DEG C, and carrying out calcining in air to obtain the cathode material lithium cuprate for the lithium-ion battery. The lithium cuprate product obtained through the method provided by the invention is fine and uniform in size; the initial specific charge capacity at the rate of 0.1C is 223-232mAh/g; the initial specific discharge capacity is 207-214mAh/g; the coulombic efficiency is 91.3%-94.7%; and the cathode material lithium cuprate for the lithium-ion battery is the cathode material for the lithium-ion battery with application value.
Description
Technical field
The invention belongs to materialogy field, relate to a kind of lithium ion battery material, specifically a kind of anode material for lithium-ion batteries copper acid lithium preparation method.
Background technology
Lithium ion battery is a kind of rechargeable battery, it have energy density high, can be with cycle charge-discharge, the advantage such as environment friendly and pollution-free so that it walks the most remote at Lu Shangyue of battery industry development, gets more and more people's extensive concerning.The first time commercialization of lithium ion battery is that Japanese Sony company in 1991 realizes, and hereafter lithium ion battery was widely used within the short time, and the equipment such as battery of mobile phone, laptop electric power and digital camera has its figure.Along with present electric automobile and the development of hybrid vehicle, the development of lithium ion battery has been pushed to another climax.Country is also to support energetically to the development of new forms of energy at present, and the appearance of various subsidy policys and the construction of key project all embody the attention of government.And positive electrode is one of important component part of lithium ion battery, research further to positive electrode is also subject to the people's attention.
The positive electrode being extensively employed now mainly has cobalt acid lithium, the LiMn2O4 of spinel structure and the ternary material etc. of the LiFePO4 of olivine structural, layer structure.And the research of copper acid lithium anode material is little with application report.
Li2CuO2For the transition metal oxide of orthorhombic structure, its space group structure is I3m, cell parameter a=3.659
A °, b=2.861 A °, c=9.387
A °, its structure also exists [CuO4] chain, this unit is present in the tetrahedron that oxygen atom is formed centered by Cu atom, and [CuO4] chain arranges in common top mode.In the course of reaction of discharge and recharge, lithium ion is from [CuO4] gap turnover between structure, this structure is that the transfer of lithium ion provides passage, and ensure that the stability of its structure.
Copper acid lithium anode material Li2CuO2For lithium-rich anode material, its discharge platform is at 2.8V, and the theoretical specific capacity of a de-lithium ion is 245mAh/g, theoretical energy density 686Wh/kg, it is intended to height compared to other positive electrode, theoretical specific capacity and theoretical energy density, is expected to be applied in electric automobile field.
The Li of rhombic system2CuO2Preparation method is mainly high temperature solid-state method, and its preparation technology is simple, but is not easily controlled granular size and pattern, and energy consumption is bigger.The lithium source of high temperature solid-state method typically uses Li2CO3, copper source uses CuO, raw material Li:Cu=2:1 by a certain percentage mixing, and through grinding raw material pulverizing mix homogeneously, in 700-850 DEG C of electric furnace, air calcination 4-24 hour i.e. can get the Li of pure phase2CuO2.N. Imanishi et al. solid sintering technology is prepared for pure phase Li2CuO2Positive electrode, first discharge specific capacity only has 100 mAh/g(Solid
State Ionics 177 (2006) 1,341 1346).This performance data can not meet application demand, needs to improve further.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of anode material for lithium-ion batteries copper acid lithium preparation method, described this anode material for lithium-ion batteries copper acid lithium preparation method to solve anode material for lithium-ion batteries copper acid lithium Li of the prior art2CuO2High temperature process heat temperature is high, the technical problem that material crystalline degree is low and chemical property is poor.
The invention provides the preparation method of a kind of anode material for lithium-ion batteries copper acid lithium, comprise the steps:
(1) first weighing Lithium hydrate, Red copper oxide and deionized water, the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 88-96:73:480-660；
(2) Lithium hydrate of 88-96 weight portion is added and the deionized water of 400 weight portions dissolves the settled solution obtaining Lithium hydrate；
(3) above-mentioned lithium hydroxide solution is added in nanon ball-mill, it is subsequently adding the Red copper oxide of 73 weight portions and the deionized water ball milling of 80-260 weight portion, the solid content controlling slurry is 25%-35%, and ball milling 3-7 hour, the particle size obtaining slurry is 270-330nm；
(4) being spray-dried after being stirred by above-mentioned ball milling product, controlling leaving air temp is 150 ~ 200 DEG C, and inlet amount 10 ~ 20ml/min obtains copper acid lithium presoma powder body.
(5) above-mentioned copper acid lithium presoma powder body after air calcination 4-8 hour, is i.e. obtained lithium ion battery copper acid lithium anode material in temperature 650-700 DEG C electric furnace.
Further, in step 4), controlling leaving air temp is 170 DEG C, and inlet amount 15ml/min obtains copper acid lithium presoma powder body.
Further, the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 92:73:660, and controlling the solid content of slurry in building-up process is 25%, and ball milling 3h, the size of suspended particle is 330nm, air calcination 4h in the electric furnace of 650 DEG C.
Further, the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 92:73:660, and controlling the solid content of slurry in building-up process is 25%, and ball milling 5h, the size of suspended particle is 300nm, air calcination 6h in the electric furnace of 680 DEG C.
Further, the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 92:73:660, and controlling the solid content of slurry in building-up process is 25%, and ball milling 7h, the size of suspended particle is 270nm, air calcination 8h in the electric furnace of 700 DEG C.
Further, the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 88:73:540, and controlling the solid content of slurry in building-up process is 30%, and ball milling 3h, the size of suspended particle is 330nm, air calcination 8h in the electric furnace of 680 DEG C.
Further, the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 88:73:540, and controlling the solid content of slurry in building-up process is 30%, and ball milling 5h, the size of suspended particle is 300nm, air calcination 4h in the electric furnace of 700 DEG C.
Further, the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 88:73:540, and controlling the solid content of slurry in building-up process is 30%, and ball milling 7h, the size of suspended particle is 270nm, air calcination 6h in the electric furnace of 650 DEG C.
Further, the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 96:73:480, and controlling the solid content of slurry in building-up process is 35%, and ball milling 3h, the size of suspended particle is 330nm, air calcination 6h in the electric furnace of 700 DEG C.
Further, the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 96:73:480, and controlling the solid content of slurry in building-up process is 35%, and ball milling 5h, the size of suspended particle is 300nm, air calcination 8h in the electric furnace of 650 DEG C.
Further, the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 96:73:480, and controlling the solid content of slurry in building-up process is 35%, and ball milling 7h, the size of suspended particle is 270nm, air calcination 4h in the electric furnace of 680 DEG C.
It is raw material that the present invention selects to use monovalence copper source Red copper oxide and Lithium hydrate, and ball milling in nanon ball-mill controls presoma particle diameter at micro-or nano size.By these measures, the solid state reaction activity of raw material can be made to improve, improve the reaction rate between raw material, effectively reduce the temperature and time of synthesis so that the product degree of crystallinity of synthesis is high, and chemical property is preferable.Gained Li2CuO2Product degree of crystallinity is high, and particle size uniformity is tiny, primary particle size 100-500 nanometer.Electrochemical property test result shows, it is thus achieved that copper acid lithium Li2CuO2Material initial charge specific capacity 223-232mAh/g under 0.1C multiplying power, first discharge specific capacity 207-214mAh/g, coulombic efficiency 91.3%-94.7%.Capability retention 87.1%-90.6% after 50 circulations, is a kind of positive electrode having potential application foreground.
The present invention compares with prior art, and its technological progress is significant.The present invention uses Red copper oxide to be copper source, uses Lithium hydrate as lithium source, is obtained by the method for high temperature process heat.The method synthesis temperature of the present invention is low, and calcination time is short, and energy consumption is low, and material crystalline degree is high, and synthesizes Li2CuO2The chemical property of material is preferable.
Accompanying drawing explanation
Fig. 1 is embodiment 1 gained anode material for lithium-ion batteries copper acid lithium Li2CuO2XRD figure spectrum.
Fig. 2 is embodiment 1 gained anode material for lithium-ion batteries copper acid lithium Li2CuO2SEM collection of illustrative plates.
Fig. 3 is embodiment 1 gained anode material for lithium-ion batteries copper acid lithium Li2CuO2Discharge and recharge collection of illustrative plates (0.1C).
Fig. 4 is embodiment 1 gained anode material for lithium-ion batteries copper acid lithium Li2CuO250 circulation volume collection of illustrative plates.
Detailed description of the invention
Below by embodiment and combine accompanying drawing the present invention is described in detail, but it is not limiting as the present invention.
The preparation of battery and electrochemical property test method:
1., the preparation of battery anode slice:
The anode material for lithium-ion batteries copper acid lithium Li that will obtain2CuO2, conductive carbon powder, organic binder bond Kynoar (PVDF) according to mass ratio 7.3:1.5:1.2 mix after obtain mixed powder, 8 grams of these mixed powders are added in 30 grams of organic solvent N-Methyl pyrrolidone (NMP), homogeneous viscous slurry is formed after being sufficiently stirred for, it is evenly applied to aluminium foil surface, air blast is put in 120 DEG C of vacuum drying ovens after drying and is dried 4h, repeatedly obtains battery anode slice after rolling.
2., battery assembles and performance test:
2016 type half-cell assessments are used to obtain Li2CuO2Chemical property.The battery pole piece rolled is stamped into the disk of diameter 12 millimeters, after its quality of precise, calculates the Li in pole piece according to formula composition2CuO2Quality, using diaphragm diameter is 19 millimeters, the negative metal lithium sheet diameter 15 millimeters of use, is assembled into and can test battery in Germany's Braun glove box.
The specific capacity test of battery uses Wuhan Lan electricity company cell tester (Land2000) to carry out.Circulation volume test is carried out repeatedly under the conditions of 0.1C.
Embodiment
1
A kind of anode material for lithium-ion batteries copper acid lithium Li2CuO2Method for preparing solid phase, specifically include following steps:
(1) first 92 parts of Lithium hydrates are added dissolving in 400 parts of deionized waters and obtain the settled solution of Lithium hydrate；
(2) being added in ball mill by the settled solution obtained by step (1), be subsequently adding 73 parts of Red copper oxides and 260 parts of deionized water ball millings, the solid content controlling slurry is 25%, and it is 270nm that ball milling 3h obtains the size of suspended particle in slurry；
(3) it is spray-dried at 170 DEG C after step (2) ball milling product being stirred, obtains presoma powder body.
(4) the presoma powder body obtained by step (3) is i.e. obtained anode material for lithium ion battery copper acid lithium Li after air calcination 4h in controlling 650 DEG C of electric furnaces of temperature2CuO2。
Use the X-ray diffractometer (XRD, Rigaku Rigaku) the anode material for lithium ion battery copper acid lithium Li to above-mentioned gained2CuO2Detecting, material testing result is as shown in Figure 1.From figure 1 it appears that all of diffraction maximum all can be demarcated as rhombic system Li in this collection of illustrative plates2CuO2Diffraction maximum, do not have the peak position of other materials to occur, and main peak intensity be high, illustrate that employing said method prepares the Li that anode material for lithium ion battery copper acid lithium is pure phase2CuO2And degree of crystallinity is preferable.
Use the scanning electron microscope (SEM, Quante2000) the anode material for lithium ion battery copper acid lithium Li to above-mentioned gained2CuO2Carry out morphology observation.From figure 2 it can be seen that the copper acid lithium Li that said method prepares2CuO2Presenting the pattern of fine uniform, primary particle size is between 100 nanometers to 500 nanometers.
By the anode material for lithium-ion batteries copper acid lithium Li of above-mentioned gained2CuO2Using half-cell method to be assembled into button-shaped 2016 batteries, test the charge-discharge performance of this battery under the multiplying power of 0.1C, Fig. 3 show the voltage-specific capacity curve of front 10 discharge and recharges.Fig. 4 show front 50 the charge-discharge performance figures of this material.It can be seen that this material initial charge specific capacity is 224mAh/g, close to the theoretical capacity of this material.First discharge specific capacity is 210 mAh/g, coulombic efficiency 91.3%.The charge specific capacity of the 2nd time is 214mAh/g, and specific discharge capacity is 208 mAh/g, and coulombic efficiency is 97.2%.After 50 times, charge specific capacity is 206mAh/g, and specific discharge capacity is 198 mAh/g, and coulombic efficiency is 96.1%, and capability retention is 88.4%.
Test result shows, the copper acid lithium Li that embodiment 1 obtains2CuO2Positive electrode has preferable chemical property, has potential using value.
Embodiment
2
A kind of anode material for lithium-ion batteries copper acid lithium Li2CuO2Method for preparing solid phase, specifically include following steps:
(1) first 92 parts of Lithium hydrates are added dissolving in 400 parts of deionized waters and obtain the settled solution of Lithium hydrate；
(2) being added in ball mill by the settled solution obtained by step (1), be subsequently adding 73 parts of Red copper oxides and 260 parts of deionized water ball millings, the solid content controlling slurry is 25%, and it is 300nm that ball milling 5h obtains the size of suspended particle in slurry；
(3) it is spray-dried at 170 DEG C after step (2) ball milling product being stirred, obtains presoma powder body.
(4) the presoma powder body obtained by step (3) is i.e. obtained anode material for lithium ion battery copper acid lithium Li after air calcination 6h in controlling 680 DEG C of electric furnaces of temperature2CuO2。
Use the X-ray diffractometer (XRD, Rigaku Rigaku) the anode material for lithium ion battery copper acid lithium Li to embodiment 2 gained2CuO2Detecting, material testing result is similar to Fig. 1, illustrates to have obtained pure phase copper acid lithium Li in embodiment 22CuO2And degree of crystallinity is preferable.
Use the scanning electron microscope (SEM, Quante2000) the copper acid lithium Li to embodiment 2 gained2CuO2Carrying out morphology observation, its result is similar to the pattern of display in Fig. 2, the copper acid lithium Li obtained2CuO2Presenting the pattern of fine uniform, size is between 100 nanometers to 500 nanometers.
By the anode material for lithium-ion batteries copper acid lithium Li of embodiment 2 gained2CuO2It is assembled into button-shaped 2016 batteries, under the multiplying power of 0.1C, testing the charge-discharge performance of this battery, its initial charge specific capacity is 232 mAh/g, close to theoretical capacity, first discharge specific capacity is 214 mAh/g, coulombic efficiency is 92.2%, and the charge specific capacity of the 50th time is 211mAh/g, and specific discharge capacity is 202mAh/g, coulombic efficiency is 95.7%, and the capability retention after 50 times is 87.1%.Test result shows, the positive electrode copper acid lithium Li that embodiment 2 obtains2CuO2There is potential using value.
Embodiment
3
A kind of anode material for lithium-ion batteries copper acid lithium Li2CuO2Method for preparing solid phase, specifically include following steps:
(1) first 92 parts of Lithium hydrates are added dissolving in 400 parts of deionized waters and obtain the settled solution of Lithium hydrate；
(2) being added in ball mill by the settled solution obtained by step (1), be subsequently adding 73 parts of Red copper oxides and 260 parts of deionized water ball millings, the solid content controlling slurry is 25%, and it is 270nm that ball milling 7h obtains the size of suspended particle in slurry；
(3) it is spray-dried at 170 DEG C after step (2) ball milling product being stirred, obtains presoma powder body.
(4) the presoma powder body obtained by step (3) is i.e. obtained anode material for lithium ion battery copper acid lithium Li after air calcination 8h in controlling 700 DEG C of electric furnaces of temperature2CuO2。
Use the X-ray diffractometer (XRD, Rigaku Rigaku) the anode material for lithium ion battery copper acid lithium Li to embodiment 3 gained2CuO2Detecting, material testing result is similar to Fig. 1, illustrates to have obtained pure phase copper acid lithium Li in embodiment 32CuO2And degree of crystallinity is preferable.
Use the scanning electron microscope (SEM, Quante2000) the copper acid lithium Li to embodiment 3 gained2CuO2Carrying out morphology observation, its result is similar to the pattern of display in Fig. 2, the copper acid lithium Li obtained2CuO2Presenting the pattern of fine uniform, size is between 100 nanometers to 500 nanometers.
By the anode material for lithium-ion batteries copper acid lithium Li of embodiment 3 gained2CuO2Being assembled into button-shaped 2016 batteries, under the multiplying power of 0.1C, test the charge-discharge performance of this battery, its initial charge specific capacity is 226mAh/g, and close to theoretical capacity, first discharge specific capacity is 213 mAh/g, and coulombic efficiency is 94.2%.The charge specific capacity of the 50th time is 208mAh/g, and specific discharge capacity is 200mAh/g, and coulombic efficiency is 96.2%, and the capability retention after 50 times is 88.5%.Test result shows, the positive electrode copper acid lithium Li that embodiment 3 obtains2CuO2There is potential using value.
Embodiment
4
A kind of anode material for lithium-ion batteries copper acid lithium Li2CuO2Method for preparing solid phase, specifically include following steps:
(1) first 88 parts of Lithium hydrates are added dissolving in 400 parts of deionized waters and obtain the settled solution of Lithium hydrate；
(2) being added in ball mill by the settled solution obtained by step (1), be subsequently adding 73 parts of Red copper oxides and 140 parts of deionized water ball millings, the solid content controlling slurry is 30%, and it is 330nm that ball milling 3h obtains the size of suspended particle in slurry；
(3) it is spray-dried at 170 DEG C after step (2) ball milling product being stirred, obtains presoma powder body.
(4) the presoma powder body obtained by step (3) is i.e. obtained anode material for lithium ion battery copper acid lithium Li after air calcination 8h in controlling 680 DEG C of electric furnaces of temperature2CuO2。
Use the X-ray diffractometer (XRD, Rigaku Rigaku) the anode material for lithium ion battery copper acid lithium Li to embodiment 4 gained2CuO2Detecting, material testing result is similar to Fig. 1, illustrates to have obtained pure phase copper acid lithium Li in embodiment 42CuO2And degree of crystallinity is preferable.
Use the scanning electron microscope (SEM, Quante2000) the copper acid lithium Li to embodiment 4 gained2CuO2Carrying out morphology observation, its result is similar to the pattern of display in Fig. 2, the copper acid lithium Li obtained2CuO2Presenting the pattern of fine uniform, size is between 100 nanometers to 500 nanometers.
By the anode material for lithium-ion batteries copper acid lithium Li of embodiment 4 gained2CuO2Being assembled into button-shaped 2016 batteries, under the multiplying power of 0.1C, test the charge-discharge performance of this battery, its initial charge specific capacity is 225mAh/g, and first discharge specific capacity is 211mAh/g, and coulombic efficiency is 93.8%.The charge specific capacity of the 50th time is 210mAh/g, and specific discharge capacity is 203mAh/g, and coulombic efficiency is 96.7%, and the capability retention after 50 times is 90.2%.Test result shows, the positive electrode copper acid lithium Li that embodiment 4 obtains2CuO2There is potential using value.
Embodiment
5
A kind of anode material for lithium-ion batteries copper acid lithium Li2CuO2Method for preparing solid phase, specifically include following steps:
(1) first 88 parts of Lithium hydrates are added dissolving in 400 parts of deionized waters and obtain the settled solution of Lithium hydrate；
(2) being added in ball mill by the settled solution obtained by step (1), be subsequently adding 73 parts of Red copper oxides and 140 parts of deionized water ball millings, the solid content controlling slurry is 30%, and it is 300nm that ball milling 5h obtains the size of suspended particle in slurry；
(3) it is spray-dried at 170 DEG C after step (2) ball milling product being stirred, obtains presoma powder body.
(4) the presoma powder body obtained by step (3) is i.e. obtained anode material for lithium ion battery copper acid lithium Li after air calcination 4h in controlling 700 DEG C of electric furnaces of temperature2CuO2。
Use the X-ray diffractometer (XRD, Rigaku Rigaku) the anode material for lithium ion battery copper acid lithium Li to embodiment 5 gained2CuO2Detecting, material testing result is similar to Fig. 1, illustrates to have obtained pure phase copper acid lithium Li in embodiment 52CuO2And degree of crystallinity is preferable.
Use the scanning electron microscope (SEM, Quante2000) the copper acid lithium Li to embodiment 5 gained2CuO2Carrying out morphology observation, its result is similar to the pattern of display in Fig. 2, the copper acid lithium Li obtained2CuO2Presenting the pattern of fine uniform, size is between 100 nanometers to 500 nanometers.
By the anode material for lithium-ion batteries copper acid lithium Li of embodiment 5 gained2CuO2Being assembled into button-shaped 2016 batteries, under the multiplying power of 0.1C, test the charge-discharge performance of this battery, its initial charge specific capacity is 227mAh/g, and first discharge specific capacity is 213mAh/g, and coulombic efficiency is 93.8%.The charge specific capacity of the 50th time is 209mAh/g, and specific discharge capacity is 201mAh/g, and coulombic efficiency is 96.2%, and the capability retention after 50 times is 88.5%.Test result shows, the positive electrode copper acid lithium Li that embodiment 5 obtains2CuO2There is potential using value.
Embodiment
6
A kind of anode material for lithium-ion batteries copper acid lithium Li2CuO2Method for preparing solid phase, specifically include following steps:
(1) first 88 parts of Lithium hydrates are added dissolving in 400 parts of deionized waters and obtain the settled solution of Lithium hydrate；
(2) being added in ball mill by the settled solution obtained by step (1), be subsequently adding 73 parts of Red copper oxides and 140 parts of deionized water ball millings, the solid content controlling slurry is 30%, and it is 270nm that ball milling 7h obtains the size of suspended particle in slurry；
(3) it is spray-dried at 170 DEG C after step (2) ball milling product being stirred, obtains presoma powder body.
(4) the presoma powder body obtained by step (3) is i.e. obtained anode material for lithium ion battery copper acid lithium Li after air calcination 6h in controlling 650 DEG C of electric furnaces of temperature2CuO2。
Use the X-ray diffractometer (XRD, Rigaku Rigaku) the anode material for lithium ion battery copper acid lithium Li to embodiment 6 gained2CuO2Detecting, material testing result is similar to Fig. 1, illustrates to have obtained pure phase copper acid lithium Li in embodiment 62CuO2And degree of crystallinity is preferable.
Use the scanning electron microscope (SEM, Quante2000) the copper acid lithium Li to embodiment 6 gained2CuO2Carrying out morphology observation, its result is similar to the pattern of display in Fig. 2, the copper acid lithium Li obtained2CuO2Presenting the pattern of fine uniform, size is between 100 nanometers to 500 nanometers.
By the anode material for lithium-ion batteries copper acid lithium Li of embodiment 6 gained2CuO2Being assembled into button-shaped 2016 batteries, under the multiplying power of 0.1C, test the charge-discharge performance of this battery, its initial charge specific capacity is 230mAh/g, and first discharge specific capacity is 212mAh/g, and coulombic efficiency is 92.2%.The charge specific capacity of the 50th time is 212mAh/g, and specific discharge capacity is 203mAh/g, and coulombic efficiency is 95.8%, and the capability retention after 50 times is 88.3%.Test result shows, the positive electrode copper acid lithium Li that embodiment 6 obtains2CuO2There is potential using value.
Embodiment
7
A kind of anode material for lithium-ion batteries copper acid lithium Li2CuO2Method for preparing solid phase, specifically include following steps:
(1) first 96 parts of Lithium hydrates are added dissolving in 400 parts of deionized waters and obtain the settled solution of Lithium hydrate；
(2) being added in ball mill by the settled solution obtained by step (1), be subsequently adding 73 parts of Red copper oxides and 80 parts of deionized water ball millings, the solid content controlling slurry is 35%, and it is 330nm that ball milling 3h obtains the size of suspended particle in slurry；
(3) it is spray-dried at 170 DEG C after step (2) ball milling product being stirred, obtains presoma powder body.
(4) the presoma powder body obtained by step (3) is i.e. obtained anode material for lithium ion battery copper acid lithium Li after air calcination 6h in controlling 700 DEG C of electric furnaces of temperature2CuO2。
Use the X-ray diffractometer (XRD, Rigaku Rigaku) the anode material for lithium ion battery copper acid lithium Li to embodiment 7 gained2CuO2Detecting, material testing result is similar to Fig. 1, illustrates to have obtained pure phase copper acid lithium Li in embodiment 72CuO2And degree of crystallinity is preferable.
Use the scanning electron microscope (SEM, Quante2000) the copper acid lithium Li to embodiment 7 gained2CuO2Carrying out morphology observation, its result is similar to the pattern of display in Fig. 2, the copper acid lithium Li obtained2CuO2Presenting the pattern of fine uniform, size is between 100 nanometers to 500 nanometers.
By the anode material for lithium-ion batteries copper acid lithium Li of embodiment 7 gained2CuO2Being assembled into button-shaped 2016 batteries, under the multiplying power of 0.1C, test the charge-discharge performance of this battery, its initial charge specific capacity is 228mAh/g, and first discharge specific capacity is 211mAh/g, and coulombic efficiency is 92.5%.The charge specific capacity of the 50th time is 212mAh/g, and specific discharge capacity is 204mAh/g, and coulombic efficiency is 96.2%, and the capability retention after 50 times is 89.5%.Test result shows, the positive electrode copper acid lithium Li that embodiment 7 obtains2CuO2There is potential using value.
Embodiment
8
A kind of anode material for lithium-ion batteries copper acid lithium Li2CuO2Method for preparing solid phase, specifically include following steps:
(1) first 92 parts of Lithium hydrates are added dissolving in 400 parts of deionized waters and obtain the settled solution of Lithium hydrate；
(2) the addition ball mill of the settled solution obtained by step (1) will carry out ball milling, be subsequently adding (1) and first 96 parts of Lithium hydrates 400 parts of deionized waters of addition will dissolve the settled solution obtaining Lithium hydrate；
(2) being added in ball mill by the settled solution obtained by step (1), be subsequently adding 73 parts of Red copper oxides and 80 parts of deionized water ball millings, the solid content controlling slurry is 35%, and it is 300nm that ball milling 5h obtains the size of suspended particle in slurry；
(3) it is spray-dried at 170 DEG C after step (2) ball milling product being stirred, obtains presoma powder body.
(4) the presoma powder body obtained by step (3) is i.e. obtained anode material for lithium ion battery copper acid lithium Li after air calcination 8h in controlling 650 DEG C of electric furnaces of temperature2CuO2。
Use the X-ray diffractometer (XRD, Rigaku Rigaku) the anode material for lithium ion battery copper acid lithium Li to embodiment 8 gained2CuO2Detecting, material testing result is similar to Fig. 1, illustrates to have obtained pure phase copper acid lithium Li in embodiment 82CuO2And degree of crystallinity is preferable.
Use the scanning electron microscope (SEM, Quante2000) the copper acid lithium Li to embodiment 8 gained2CuO2Carrying out morphology observation, its result is similar to the pattern of display in Fig. 2, the copper acid lithium Li obtained2CuO2Presenting the pattern of fine uniform, size is between 100 nanometers to 500 nanometers.
By the anode material for lithium-ion batteries copper acid lithium Li of embodiment 8 gained2CuO2Being assembled into button-shaped 2016 batteries, under the multiplying power of 0.1C, test the charge-discharge performance of this battery, its initial charge specific capacity is 225mAh/g, and first discharge specific capacity is 213mAh/g, and coulombic efficiency is 94.7%.The charge specific capacity of the 50th time is 209mAh/g, and specific discharge capacity is 202mAh/g, and coulombic efficiency is 96.7%, and the capability retention after 50 times is 89.8%.Test result shows, the positive electrode copper acid lithium Li that embodiment 8 obtains2CuO2There is potential using value.
Embodiment
9
A kind of anode material for lithium-ion batteries copper acid lithium Li2CuO2Method for preparing solid phase, specifically include following steps:
(1) first 96 parts of Lithium hydrates are added dissolving in 400 parts of deionized waters and obtain the settled solution of Lithium hydrate；
(2) being added in ball mill by the settled solution obtained by step (1), be subsequently adding 73 parts of Red copper oxides and 80 parts of deionized water ball millings, the solid content controlling slurry is 35%, and it is 270nm that ball milling 7h obtains the size of suspended particle in slurry；
(3) it is spray-dried at 170 DEG C after step (2) ball milling product being stirred, obtains presoma powder body.
(4) the presoma powder body obtained by step (3) is i.e. obtained anode material for lithium ion battery copper acid lithium Li after air calcination 4h in controlling 680 DEG C of electric furnaces of temperature2CuO2。
Use the X-ray diffractometer (XRD, Rigaku Rigaku) the anode material for lithium ion battery copper acid lithium Li to embodiment 9 gained2CuO2Detecting, material testing result is similar to Fig. 1, illustrates to have obtained pure phase copper acid lithium Li in embodiment 92CuO2And degree of crystallinity is preferable.
Use the scanning electron microscope (SEM, Quante2000) the copper acid lithium Li to embodiment 9 gained2CuO2Carrying out morphology observation, its result is similar to the pattern of display in Fig. 2, the copper acid lithium Li obtained2CuO2Presenting the pattern of fine uniform, size is between 100 nanometers to 500 nanometers.
By the anode material for lithium-ion batteries copper acid lithium Li of embodiment 9 gained2CuO2Being assembled into button-shaped 2016 batteries, under the multiplying power of 0.1C, test the charge-discharge performance of this battery, its initial charge specific capacity is 223mAh/g, and first discharge specific capacity is 207mAh/g, and coulombic efficiency is 92.8%.The charge specific capacity of the 50th time is 212mAh/g, and specific discharge capacity is 202mAh/g, and coulombic efficiency is 95.2%, and the capability retention after 50 times is 90.6%.Test result shows, the positive electrode copper acid lithium Li that embodiment 9 obtains2CuO2There is potential using value.
In sum, a kind of anode material for lithium ion battery copper acid lithium Li of the present invention2CuO2Method for preparing solid phase, use Red copper oxide and Lithium hydrate as raw material, control feedstock Particle size by nano ball grinding technique so that materials synthesis temperature reduces, calcination time shortens, and product grain is the most tiny and degree of crystallinity is higher.Electrochemical results shows, the Li of the method synthesis2CuO2Material is as anode material for lithium ion battery, initial charge specific capacity 223-232mAh/g under 0.1C multiplying power, first discharge specific capacity 207-214mAh/g, coulombic efficiency 91.3%-94.7%.Capability retention 87.1%-90.6% after 50 circulations.The positive electrode copper acid lithium Li that the present invention obtains2CuO2There is potential using value.
Foregoing is only the basic explanation under present inventive concept, and according to any equivalent transformation that technical scheme is made, all should belong to protection scope of the present invention.
Claims (10)
1. the preparation method of an anode material for lithium-ion batteries copper acid lithium, it is characterised in that comprise the steps:
(1) first weighing Lithium hydrate, Red copper oxide and deionized water, the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 88-96:73:480-660；
(2) Lithium hydrate of 88-96 weight portion is added and the deionized water of 400 weight portions dissolves the settled solution obtaining Lithium hydrate；
(3) above-mentioned lithium hydroxide solution is added in nanon ball-mill, it is subsequently adding the Red copper oxide of 73 weight portions and the deionized water ball milling of 80-260 weight portion, the solid content controlling slurry is 25%-35%, and ball milling 3-7 hour, the particle size obtaining slurry is 270-330nm；
(4) being spray-dried after being stirred by above-mentioned ball milling product, controlling leaving air temp is 150 ~ 200 DEG C, and inlet amount 10 ~ 20ml/min obtains copper acid lithium presoma powder body；
(5) above-mentioned copper acid lithium presoma powder body after air calcination 4-8 hour, is i.e. obtained lithium ion battery copper acid lithium anode material in temperature 650-700 DEG C electric furnace.
The preparation method of a kind of anode material for lithium-ion batteries copper acid lithium the most according to claim 1, it is characterized in that: the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 92:73:660, controlling the solid content of slurry in building-up process is 25%, ball milling 3h, the size of suspended particle is 330nm, air calcination 4h in the electric furnace of 650 DEG C.
The preparation method of a kind of anode material for lithium-ion batteries copper acid lithium the most according to claim 1, it is characterized in that: the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 92:73:660, controlling the solid content of slurry in building-up process is 25%, ball milling 5h, the size of suspended particle is 300nm, air calcination 6h in the electric furnace of 680 DEG C.
The preparation method of a kind of anode material for lithium-ion batteries copper acid lithium the most according to claim 1, it is characterized in that: the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 92:73:660, controlling the solid content of slurry in building-up process is 25%, ball milling 7h, the size of suspended particle is 270nm, air calcination 8h in the electric furnace of 700 DEG C.
The preparation method of a kind of anode material for lithium-ion batteries copper acid lithium the most according to claim 1, it is characterized in that: the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 88:73:540, controlling the solid content of slurry in building-up process is 30%, ball milling 3h, the size of suspended particle is 330nm, air calcination 8h in the electric furnace of 680 DEG C.
The preparation method of a kind of anode material for lithium-ion batteries copper acid lithium the most according to claim 1, it is characterized in that: the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 88:73:540, controlling the solid content of slurry in building-up process is 30%, ball milling 5h, the size of suspended particle is 300nm, air calcination 4h in the electric furnace of 700 DEG C.
The preparation method of a kind of anode material for lithium-ion batteries copper acid lithium the most according to claim 1, it is characterized in that: the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 88:73:540, controlling the solid content of slurry in building-up process is 30%, ball milling 7h, the size of suspended particle is 270nm, air calcination 6h in the electric furnace of 650 DEG C.
The preparation method of a kind of anode material for lithium-ion batteries copper acid lithium the most according to claim 1, it is characterized in that: the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 96:73:480, controlling the solid content of slurry in building-up process is 35%, ball milling 3h, the size of suspended particle is 330nm, air calcination 6h in the electric furnace of 700 DEG C.
The preparation method of a kind of anode material for lithium-ion batteries copper acid lithium the most according to claim 1, it is characterized in that: the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 96:73:480, controlling the solid content of slurry in building-up process is 35%, ball milling 5h, the size of suspended particle is 300nm, air calcination 8h in the electric furnace of 650 DEG C.
The preparation method of a kind of anode material for lithium-ion batteries copper acid lithium the most according to claim 1, it is characterized in that: the mass ratio of described Lithium hydrate, Red copper oxide and deionized water is 96:73:480, controlling the solid content of slurry in building-up process is 35%, ball milling 7h, the size of suspended particle is 270nm, air calcination 4h in the electric furnace of 680 DEG C.
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