CN101552332A - Method for preparing cathode material LiCo*Ni*Mn*O* of lithium ion battery using carbon dioxide as catalyst - Google Patents
Method for preparing cathode material LiCo*Ni*Mn*O* of lithium ion battery using carbon dioxide as catalyst Download PDFInfo
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- CN101552332A CN101552332A CNA2009100721165A CN200910072116A CN101552332A CN 101552332 A CN101552332 A CN 101552332A CN A2009100721165 A CNA2009100721165 A CN A2009100721165A CN 200910072116 A CN200910072116 A CN 200910072116A CN 101552332 A CN101552332 A CN 101552332A
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Abstract
The present invention provides a method for preparing cathode material LiCo*Ni*Mn*O* of lithium ion battery using carbon dioxide as catalyst, and relates to a method for preparing cathode material of lithium ion battery. The method of the invention settles the problems of inferior crystallinity degree and few cycle numbers of charging/discharging caused by inferior alkaline of carbonate solution in prior method. The method of the invention comprises the following steps: 1. dissolving cobalt slat, nickel salt and manganese salt in distilled water for obtaining a system 1; 2. dissolving sodium carbonate and ammonia water in distilled water for obtaining a system 2; 3. adding the system 1 and system 2 into the distilled water, filtering, drying the filter residue and obtaining the precursor powder; and 4. after mixing a lithium source with the precursor powder, sintering and obtaining the cathode material of lithium ion battery. The cathode material of lithium ion battery, which is prepared according to the invention, has the advantages of high crystallinity degree and high discharge capacity. Furthermore the capacity retention rate of cathode material of lithium ion battery, which is prepared according to the invention, obtains 98.6% after cycling for 30 times.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries.
Background technology
The anode material for lithium-ion batteries of being developed at present has a lot of systems, its laminate lithium transition-metal oxide system (LiCo
xNi
yMn
zO
2, 0≤x, y, z≤1) and have advantages such as stable performance, fail safe height, coprecipitation method is the important method of preparation lithium transition-metal oxide series electrode material, in coprecipitation method, is called the carbonate coprecipitation method with carbonate again as precipitation reagent.Because carbonate can form stable dicovalent carbon hydrochlorate with transition metal, avoided transition metal by further oxidation.But, because the alkalescence of carbonate solution is lower, the Ph value of solution is lower in course of reaction, and part ion not exclusively precipitates in the course of reaction, cause prepared positive electrode degree of crystallinity poor, the positive discharge capacity of gained positive electrode preparation is low, the charge and discharge cycles number of times is few.
Summary of the invention
Technical problem to be solved by this invention is to hang down for the alkalescence that solves carbonate solution in the existing method to cause positive electrode degree of crystallinity poor, the problem that the positive discharge capacity is low, the charge and discharge cycles number of times is few provides a kind of and has prepared anode material for lithium-ion batteries LiCo with carbon dioxide as catalyst
xNi
yMn
zO
2Method.
The present invention prepares anode material for lithium-ion batteries LiCo with carbon dioxide as catalyst
xNi
yMn
zO
2Method as follows: one, according to chemical formula LiCo
xNi
yMn
zO
2, be that the ratio of x: y: z takes by weighing cobalt salt, nickel salt and manganese salt respectively in Li element, Ni element and Mn element mol ratio, be dissolved in then in the distilled water, obtain system 1,0≤x wherein, 0≤y, z≤1, x, y, z are not 0 simultaneously; Two, sodium carbonate and ammoniacal liquor are dissolved in the distilled water, obtain system 2, wherein cobalt ions, nickel ion and the total amount of substance of manganese ion are (x+y+z) with sodium carbonate amount of substance ratio in the system 1: 1; Three, be that 30 ℃～60 ℃, pH value are under 8～9 the condition system 1 and system 2 to be joined in the distilled water in carbon dioxide atmosphere, water temperature, then low whipping speed be stir under 500～1000 rev/mins the condition 12 hours, filter, be the sequence alternate washing 3 times of 95% ethanol and distilled water washing again with the filter residue mass concentration, with filter residue be then again in room temperature, vacuum degree-condition of 0.1MPa under dry 10 hours, obtain the precursor powder; Four, with lithium source and precursor powder by 1～1.3: 1 mol ratio ball milling mixed 2～6 hours, and sintering 10 hours under 600 ℃～900 ℃ condition promptly gets anode material for lithium-ion batteries LiCo again
xNi
yMn
zO
2Wherein the concentration of cobalt salt is 0.5～2mol/L in the step 1 system 1; System 1 is 1: 1 with the volume ratio of system 2 in the step 3, and the volume ratio of distilled water and system 1 is 2.5～10: 1.
Cobalt salt described in the step 1 of the present invention is a kind of or wherein several combination in cobaltous sulfate, cobalt acetate and the cobalt nitrate; Nickel salt described in the step 1 is a kind of or wherein several combination in nickelous sulfate, nickel acetate and the nickel nitrate; Manganese salt described in the step 1 is a kind of or wherein several combination in manganese sulfate, manganese acetate and the manganese nitrate; The concentration of ammoniacal liquor is 0.1～0.5mol/L in the step 2; Lithium source described in the step 4 is lithium carbonate or lithium hydroxide; The material ratio of ball milling is 10: 1 in the step 4.
The present invention adopts carbon dioxide as catalyst, carbon dioxide is partially soluble in reaction solution, both improve the concentration of carbanion in the reaction solution, reduced the survivor ion amount in the reaction solution, avoid transition metal ions oxidized again, thereby improved the purity and the degree of crystallinity of electrode material; Adopt ammoniacal liquor as chelating agent, form uniform intermediate, improved the uniformity of material with transition metal ions.
The anode material for lithium-ion batteries LiCo that the present invention makes
xNi
yMn
zO
2Than degree of crystallinity height, the discharge capacity height of the cell positive material that does not adopt carbon dioxide to make as catalyst, reached 98.6% at the capability retention that discharges and recharges the anode material for lithium-ion batteries that 30 circulation back the present invention make.
Description of drawings
Fig. 1 is the X-ray diffractogram of embodiment 70 gained cell positive materials.Fig. 2 is the X-ray diffractogram of embodiment 71 gained anode material for lithium-ion batteries.Fig. 3 is the discharge curve of embodiment 70 gained cell positive materials.Fig. 4 is the discharge curve of embodiment 71 gained anode material for lithium-ion batteries.Fig. 5 is the cycle performance curve chart of embodiment 70 gained cell positive materials.Fig. 6 is the cycle performance curve chart of embodiment 71 gained anode material for lithium-ion batteries.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: present embodiment prepares anode material for lithium-ion batteries LiCo with carbon dioxide as catalyst
xNi
yMn
zO
2Method as follows: one, according to chemical formula LiCo
xNi
yMn
zO
2, be that the ratio of x: y: z takes by weighing cobalt salt, nickel salt and manganese salt respectively in Li element, Ni element and Mn element mol ratio, be dissolved in then in the distilled water, obtain system 1,0≤x wherein, 0≤y, z≤1, x, y, z are not 0 simultaneously; Two, sodium carbonate and ammoniacal liquor are dissolved in the distilled water, obtain system 2, wherein cobalt ions, nickel ion and the total amount of substance of manganese ion are (x+y+z) with sodium carbonate amount of substance ratio in the system 1: 1; Three, be that 30 ℃～60 ℃, pH value are under 8～9 the condition system 1 and system 2 to be joined in the distilled water in carbon dioxide atmosphere, water temperature, then low whipping speed be stir under 500～1000 rev/mins the condition 12 hours, filter, be the sequence alternate washing 3 times of 95% ethanol and distilled water washing again with the filter residue mass concentration, with filter residue be then again in room temperature, vacuum degree-condition of 0.1MPa under dry 10 hours, obtain the precursor powder; Four, with lithium source and precursor powder by 1～1.3: 1 mol ratio ball milling mixed 2～6 hours, and sintering 10 hours under 600 ℃～900 ℃ condition promptly gets anode material for lithium-ion batteries LiCo again
xNi
yMn
zO
2Wherein the concentration of cobalt salt is 0.5～2mol/L in the step 1 system 1; System 1 is 1: 1 with the volume ratio of system 2 in the step 3, and the volume ratio of distilled water and system 1 is 2.5～10: 1.
Present embodiment balls grinding machine is the planetary ball mill of the QM-3SP04 of Nanjing Univ. Instrument Factory's production.
Embodiment two: what present embodiment and embodiment one were different is that the cobalt salt described in the step 1 is cobaltous sulfate, cobalt acetate or cobalt nitrate.Other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is that the cobalt salt described in the step 1 is a composition any two kinds in cobaltous sulfate, cobalt acetate and the cobalt nitrate.Other is identical with embodiment one.
Two kinds of compositions are pressed arbitrarily than mixing in the cobalt salt described in the present embodiment.
Embodiment four: what present embodiment and embodiment one were different is that the nickel salt described in the step 1 is the composition of nickelous sulfate, nickel acetate and nickel nitrate.Other is identical with embodiment one.
Three kinds of compositions are pressed arbitrarily than mixing in the cobalt salt described in the present embodiment.
Embodiment five: what present embodiment and embodiment one, two, three or four were different is that the nickel salt described in the step 1 is nickelous sulfate, nickel acetate or nickel nitrate.Other is identical with embodiment one, two, three or four.
Embodiment six: what present embodiment and embodiment one, two, three or four were different is that the nickel salt described in the step 1 is a composition any two kinds in nickelous sulfate, nickel acetate and the nickel nitrate.Other is identical with embodiment one, two, three or four.
Two kinds of compositions are pressed arbitrarily than mixing in the nickel salt described in the present embodiment.
Embodiment seven: what present embodiment and embodiment one, two, three or four were different is that the nickel salt described in the step 1 is the composition of nickelous sulfate, nickel acetate and nickel nitrate.Other is identical with embodiment one, two, three or four.
Three kinds of compositions are pressed arbitrarily than mixing in the nickel salt described in the present embodiment.
Embodiment eight: what present embodiment and embodiment five, six or seven were different is that the manganese salt described in the step 1 is manganese sulfate, manganese acetate or manganese nitrate.Other is identical with embodiment five, six or seven.
Embodiment nine: what present embodiment and embodiment five, six or seven were different is that the manganese salt described in the step 1 is composition any two kinds in manganese sulfate, manganese acetate and the manganese nitrate.Other is identical with embodiment five, six or seven.
Two kinds of compositions are pressed arbitrarily than mixing in the manganese salt described in the present embodiment.
Embodiment ten: what present embodiment and embodiment five, six or seven were different is that the manganese salt described in the step 1 is the composition of manganese sulfate, manganese acetate and manganese nitrate.Other is identical with embodiment five, six or seven.
Three kinds of compositions are pressed arbitrarily than mixing in the manganese salt described in the present embodiment.
Embodiment 11: present embodiment and embodiment one, two, three, four, eight, nine or ten are different is that the concentration of ammoniacal liquor in the step 2 is 0.1～0.5mol/L.Other is identical with embodiment one, two, three, four, eight, nine or ten.
Embodiment 12: what present embodiment and embodiment 11 were different is that water temperature is 50 ℃ in the step 3.Other is identical with embodiment 11.
Embodiment 13: what present embodiment and embodiment one, two, three, four, eight, nine, ten or 12 were different is that mixing speed is 800 rev/mins in the step 3.Other is identical with embodiment one, two, three, four, eight, nine, ten or 12.
Embodiment 14: what present embodiment and embodiment 13 were different is that the lithium source described in the step 4 is lithium carbonate or lithium hydroxide.Other is identical with embodiment 13.
Embodiment 15: present embodiment and embodiment one, two, three, four, eight, nine, ten, 12 or 14 are different is that the material ratio of ball milling in the step 4 is 10: 1.Other is identical with embodiment one, two, three, four, eight, nine, ten, 12 or 14.
Embodiment 16: what present embodiment and embodiment 15 were different is that sintering temperature is 850 ℃ in the step 4.Other is identical with embodiment 15.
Embodiment 17: present embodiment and embodiment one are different is that the concentration of cobalt salt in the step 1 system 1 is 0.8～1.8mol/L.Other is identical with embodiment one.
Embodiment 18: present embodiment and embodiment one are different is that the concentration of cobalt salt in the step 1 system 1 is 0.9～1.6mol/L.Other is identical with embodiment one.
Embodiment 19: present embodiment and embodiment one are different is that the concentration of cobalt salt in the step 1 system 1 is 1～1.5mol/L.Other is identical with embodiment one.
Embodiment 20: present embodiment and embodiment one are different is that the concentration of cobalt salt in the step 1 system 1 is 1.3mol/L.Other is identical with embodiment one, and other is identical with embodiment one.
Embodiment 21: present embodiment and embodiment one are different is that the concentration of nickel salt in the step 1 system 1 is 0.8～1.8mol/L.Other is identical with embodiment one.
Embodiment 22: present embodiment and embodiment one are different is that the concentration of nickel salt in the step 1 system 1 is 0.9～1.6mol/L.Other is identical with embodiment one.
Embodiment 23: present embodiment and embodiment one are different is that the concentration of nickel salt in the step 1 system 1 is 1～1.5mol/L.Other is identical with embodiment one.
Embodiment 24: present embodiment and embodiment one are different is that the concentration of nickel salt in the step 1 system 1 is 1.3mol/L.Other is identical with embodiment one.
Embodiment 25: present embodiment and embodiment one are different is that the concentration of manganese salt in the step 1 system 1 is 0.8～1.8mol/L.Other is identical with embodiment one.
Embodiment 26: present embodiment and embodiment one are different is that the concentration of manganese salt in the step 1 system 1 is 0.9～1.6mol/L.Other is identical with embodiment one.
Embodiment 27: present embodiment and embodiment one are different is that the concentration of manganese salt in the step 1 system 1 is 1～1.5mol/L.Other is identical with embodiment one.
Embodiment 28: present embodiment and embodiment one are different is that the concentration of manganese salt in the step 1 system 1 is 1.3mol/L.Other is identical with embodiment one.
Embodiment 29: present embodiment and embodiment one are different is that the concentration of cobalt salt in the step 1 system 1 is 0.8～1.8mol/L, and the concentration of nickel salt is 0.9～1.7mol/L, and the concentration of manganese salt is 0.6～1.7mol/L.Other is identical with embodiment one.
Embodiment 30: present embodiment and embodiment one are different is that the concentration of cobalt salt in the step 1 system 1 is 1～1.7mol/L, and the concentration of nickel salt is 1～1.6mol/L, and the concentration of manganese salt is 1～1.5mol/L.Other is identical with embodiment one.
Embodiment 31: present embodiment and embodiment one are different is that the concentration of cobalt salt in the step 1 system 1 is 1.2～1.5mol/L, and the concentration of nickel salt is 1.1～1.5mol/L, and the concentration of manganese salt is 1.1～1.4mol/L.Other is identical with embodiment one.
Embodiment 32: present embodiment and embodiment one are different is that the concentration of cobalt salt in the step 1 system 1 is 1.4mol/L, and the concentration of nickel salt is 1.3mol/L, and the concentration of manganese salt is 1.2mol/L.Other is identical with embodiment one.
Embodiment 33: present embodiment and embodiment one are different is that the concentration of ammoniacal liquor in the step 2 is 0.15～0.45mol/L.Other is identical with embodiment one.
Embodiment 34: present embodiment and embodiment one are different is that the concentration of ammoniacal liquor in the step 2 is 0.2～0.4mol/L.Other is identical with embodiment one.
Embodiment 35: present embodiment and embodiment one are different is that the concentration of ammoniacal liquor in the step 2 is 0.3mol/L.Other is identical with embodiment one.
Embodiment 36: present embodiment and embodiment one are different is that the mol ratio of sodium carbonate and ammoniacal liquor is 5.5～9.5: 1 in the step 2.Other is identical with embodiment one.
Embodiment 37: present embodiment and embodiment one are different is that the mol ratio of sodium carbonate and ammoniacal liquor is 6～9: 1 in the step 2.Other is identical with embodiment one.
Embodiment 38: present embodiment and embodiment one are different is that the mol ratio of sodium carbonate and ammoniacal liquor is 6.5～8.5: 1 in the step 2.Other is identical with embodiment one.
Embodiment 39: present embodiment and embodiment one are different is that the mol ratio of sodium carbonate and ammoniacal liquor is 7～8: 1 in the step 2.Other is identical with embodiment one.
Embodiment 40: present embodiment and embodiment one are different is that the mol ratio of sodium carbonate and ammoniacal liquor is 7.5: 1 in the step 2.Other is identical with embodiment one.
Embodiment 41: present embodiment and embodiment one are different is that water temperature in the step 3 is 35 ℃～55 ℃.Other is identical with embodiment one.
Embodiment 42: present embodiment and embodiment one are different is that water temperature in the step 3 is 38 ℃～51 ℃.Other is identical with embodiment one.
Embodiment 43: present embodiment and embodiment one are different is that water temperature in the step 3 is 42 ℃～48 ℃.Other is identical with embodiment one.
Embodiment 44: present embodiment and embodiment one are different is that water temperature in the step 3 is 45 ℃.Other is identical with embodiment one.
Embodiment 45: present embodiment and embodiment one are different is that pH value in the step 3 is 8.5.Other is identical with embodiment one.
Embodiment 46: present embodiment and embodiment one are different is that mixing speed in the step 3 is 550～950 rev/mins.Other is identical with embodiment one.
Embodiment 47: present embodiment and embodiment one are different is that mixing speed in the step 3 is 600～900 rev/mins.Other is identical with embodiment one.
Embodiment 48: present embodiment and embodiment one are different is that mixing speed in the step 3 is 650～850 rev/mins.Other is identical with embodiment one.
Embodiment 49: present embodiment and embodiment one are different is that mixing speed in the step 3 is 700～840 rev/mins.Other is identical with embodiment one.
Embodiment 50: present embodiment and embodiment one are different is that mixing speed in the step 3 is 750 rev/mins.Other is identical with embodiment one.
Embodiment 51: present embodiment and embodiment one are different is that the volume ratio of distilled water and system 1 is 3～9.5: 1 in the step 3.Other is identical with embodiment one.
Embodiment 52: present embodiment and embodiment one are different is that the volume ratio of distilled water and system 1 is 3.5～9: 1 in the step 3.Other is identical with embodiment one.
Embodiment 53: present embodiment and embodiment one are different is that the volume ratio of distilled water and system 1 is 4～8.5: 1 in the step 3.Other is identical with embodiment one.
Embodiment 54: present embodiment and embodiment one are different is that the volume ratio of distilled water and system 1 is 4.5～8: 1 in the step 3.Other is identical with embodiment one.
Embodiment 55: present embodiment and embodiment one are different is that the volume ratio of distilled water and system 1 is 5～7.5: 1 in the step 3.Other is identical with embodiment one.
Embodiment 56: present embodiment and embodiment one are different is that the volume ratio of distilled water and system 1 is 5.5～7: 1 in the step 3.Other is identical with embodiment one.
Embodiment 57: present embodiment and embodiment one are different is that the volume ratio of distilled water and system 1 is 6: 1 in the step 3.Other is identical with embodiment one.
Embodiment 58: present embodiment and embodiment one are different is that the volume ratio of distilled water and system 1 is 6.5: 1 in the step 3.Other is identical with embodiment one.
Embodiment 59: present embodiment and embodiment one are different is that the mol ratio of lithium source and precursor powder is 1.2: 1 in the step 4.Other is identical with embodiment one.
Embodiment 60: what present embodiment and embodiment one were different is that the ball milling incorporation time is 2.5～5.5 hours in the step 4.Other is identical with embodiment one.
Embodiment 61: what present embodiment and embodiment one were different is that the ball milling incorporation time is 3～5 hours in the step 4.Other is identical with embodiment one.
Embodiment 62: what present embodiment and embodiment one were different is that the ball milling incorporation time is 4 hours in the step 4.Other is identical with embodiment one.
Embodiment 63: what present embodiment and embodiment one were different is that the ball milling incorporation time is 4.5 hours in the step 4.Other is identical with embodiment one.
Embodiment 64: what present embodiment and embodiment one were different is that sintering temperature is 680 ℃～880 ℃ in the step 4.Other is identical with embodiment one.
Embodiment 65: what present embodiment and embodiment one were different is that sintering temperature is 700 ℃～870 ℃ in the step 4.Other is identical with embodiment one.
Embodiment 66: what present embodiment and embodiment one were different is that sintering temperature is 720 ℃～860 ℃ in the step 4.Other is identical with embodiment one.
Embodiment 67: what present embodiment and embodiment one were different is that sintering temperature is 750 ℃～830 ℃ in the step 4.Other is identical with embodiment one.
Embodiment 68: what present embodiment and embodiment one were different is that sintering temperature is 780 ℃～810 ℃ in the step 4.Other is identical with embodiment one.
Embodiment 69: what present embodiment and embodiment one were different is that sintering temperature is 800 ℃ in the step 4.Other is identical with embodiment one.
Embodiment 70: the preparation method of cell positive material is as follows in the present embodiment: one, with 56.22g CoSO
4H
2O, 52.57g NiSO
4H
2O and 33.80g MnSO
4H
2O is dissolved in the 200mL water, obtains system 1; Two, be the NH of 0.5mol/L with 171.69g NaOH and 6.54g concentration
3H
2O is dissolved in the 200mL water, obtains system 2; Three, in reactor water temperature to keep 40 ℃, pH be under 8 the condition, splash in reactor that 1500mL distilled water is housed with 1000 rev/mins mixing speed system 1 and system 2 and stir 12 hours, filter, again with filter residue according to being that 95% ethanol washing is washed 3 times with the sequence alternate of distilled water washing more earlier with mass concentration, with filter residue be then again in room temperature, vacuum degree-condition of 0.1MPa under dry 10 hours, obtain the precursor powder; Four, with 27.70g LiOHH
2O mixes with precursor powder ball milling and obtained mixture in 5 hours, with mixture sintering 10 hours under 850 ℃ condition, promptly gets anode material for lithium-ion batteries again.
With present embodiment gained positive electrode, acetylene black and polyvinylidene fluoride are according to positive electrode: acetylene black: polyvinylidene fluoride is that 80: 10: 10 quality was mixed 5 hours than ball milling, then mixture is coated in 95% ethanol and cleaned on three times the aluminium foil, the aluminium foil that will scribble mixture is again dried under 100 ℃ condition, compression moulding under the 20MPa, obtain positive pole, be negative pole then with the lithium metal, the BLE-5T type electrolyte that Beijing Inst. of Chemical Reagent produces is electrolyte, be assembled into the CR2032 button cell, the model that adopts Shenzhen City, Guangdong Province new Weir Electronics Co., Ltd. to produce then is to carry out the constant current charge-discharge test on the button cell charge-discharge test instrument of BTS, and wherein voltage range is 2.8V～4.5V.
The used ball mill of present embodiment is the planetary ball mill of the QM-3SP04 of Nanjing Univ. Instrument Factory's production.
Embodiment 71: the preparation method of anode material for lithium-ion batteries is as follows in the present embodiment: one, with 56.22g CoSO
4H
2O, 52.57g NiSO
4H
2O and 33.80g MnSO
4H
2O is dissolved in the 200mL water, obtains system 1; Two, be the NH of 0.5mol/L with 171.69g NaOH and 6.54g concentration
3H
2O is dissolved in the 200mL water, obtains system 2; Three, the carbon dioxide feeding is equipped with in the reactor of 1500mL distilled water, 40 ℃ of water temperature maintenances, pH are 8, keep feeding under the condition of carbon dioxide in reactor, splash in reactor with 1000 rev/mins mixing speed system 1 and system 2 and stir 12 hours, filter, again with filter residue according to being that 95% ethanol washing is washed 3 times with the sequence alternate of distilled water washing more earlier with mass concentration, with filter residue be then again in room temperature, vacuum degree-condition of 0.1MPa under dry 10 hours, obtain the precursor powder; Four, with 27.70g LiOHH
2O mixes with precursor powder ball milling and obtained mixture in 5 hours, with mixture sintering 10 hours under 850 ℃ condition, promptly gets anode material for lithium-ion batteries again.
With present embodiment gained positive electrode, acetylene black and polyvinylidene fluoride are according to positive electrode: acetylene black: polyvinylidene fluoride is that 80: 10: 10 quality was mixed 5 hours than ball milling, then mixture is coated in 95% ethanol and cleaned on three times the aluminium foil, the aluminium foil that will scribble mixture is again dried under 100 ℃ condition, compression moulding under the 20MPa, obtain positive pole, be negative pole then with the lithium metal, the BLE-5T type electrolyte that Beijing Inst. of Chemical Reagent produces is electrolyte, be assembled into the CR2032 button cell, the model that adopts Shenzhen City, Guangdong Province new Weir Electronics Co., Ltd. to produce then is to carry out the constant current charge-discharge test on the button cell charge-discharge test instrument of BTS, and wherein voltage range is 2.8V～4.5V.
The used ball mill of present embodiment is the planetary ball mill of the QM-3SP04 of Nanjing Univ. Instrument Factory's production.
By Fig. 1 (X-ray diffractogram of embodiment 70 gained cell positive materials.) and the contrast of Fig. 2 (X-ray diffractogram of present embodiment gained anode material for lithium-ion batteries) as can be known, the degree of crystallinity of present embodiment gained anode material for lithium-ion batteries is than the degree of crystallinity height of embodiment 70 gained cell positive materials; By the contrast of Fig. 3 (discharge curves of embodiment 70 gained cell positive materials) and Fig. 4 (discharge curve of present embodiment gained anode material for lithium-ion batteries) as can be known, the discharge capacity of present embodiment gained anode material for lithium-ion batteries and discharge platform are all than the discharge capacity and the discharge platform height of embodiment 70 gained cell positive materials; By Fig. 5 (the cycle performance curve charts of embodiment 70 gained cell positive materials) and Fig. 6 (the cycle performance curve chart of present embodiment gained anode material for lithium-ion batteries) as can be known, capability retention at 30 circulation back present embodiment gained anode material for lithium-ion batteries has reached 98.6%, and the capability retention of embodiment 70 gained cell positive materials only is 95.5%, illustrates that present embodiment gained anode material for lithium-ion batteries is than embodiment 70 gained cell positive material good cycle.
Claims (10)
1, prepares anode material for lithium-ion batteries LiCo with carbon dioxide as catalyst
xNi
yMn
zO
2Method, it is characterized in that preparing anode material for lithium-ion batteries LiCo with carbon dioxide as catalyst
xNi
yMn
zO
2Method as follows: one, according to chemical formula LiCo
xNi
yMn
zO
2, be that the ratio of x: y: z takes by weighing cobalt salt, nickel salt and manganese salt respectively in Li element, Ni element and Mn element mol ratio, be dissolved in then in the distilled water, obtain system 1,0≤x wherein, 0≤y, z≤1, x, y, z are not 0 simultaneously; Two, sodium carbonate and ammoniacal liquor are dissolved in the distilled water, obtain system 2, wherein cobalt ions, nickel ion and the total amount of substance of manganese ion are (x+y+z) with sodium carbonate amount of substance ratio in the system 1: 1; Three, be that 30 ℃～60 ℃, pH value are under 8～9 the condition system 1 and system 2 to be joined in the distilled water in carbon dioxide atmosphere, water temperature, then low whipping speed be stir under 500～1000 rev/mins the condition 12 hours, filter, be the sequence alternate washing 3 times of 95% ethanol and distilled water washing again with the filter residue mass concentration, with filter residue be then again in room temperature, vacuum degree-condition of 0.1MPa under dry 10 hours, obtain the precursor powder; Four, with lithium source and precursor powder by 1～1.3: 1 mol ratio ball milling mixed 2～6 hours, and sintering 10 hours under 600 ℃～900 ℃ condition promptly gets anode material for lithium-ion batteries LiCo again
xNi
yMn
zO
2Wherein the concentration of cobalt salt is 0.5～2mol/L in the step 1 system 1; System 1 is 1: 1 with the volume ratio of system 2 in the step 3, and the volume ratio of distilled water and system 1 is 2.5～10: 1.
2, according to claim 1ly prepare anode material for lithium-ion batteries LiCo with carbon dioxide as catalyst
xNi
yMn
zO
2Method, it is characterized in that the cobalt salt described in the step 1 is a kind of or wherein several combination in cobaltous sulfate, cobalt acetate and the cobalt nitrate.
3, according to claim 1 and 2ly prepare anode material for lithium-ion batteries LiCo with carbon dioxide as catalyst
xNi
yMn
zO
2Method, it is characterized in that the nickel salt described in the step 1 is a kind of or wherein several combination in nickelous sulfate, nickel acetate and the nickel nitrate.
4, according to claim 3ly prepare anode material for lithium-ion batteries LiCo with carbon dioxide as catalyst
xNi
yMn
zO
2Method, it is characterized in that the manganese salt described in the step 1 is a kind of or wherein several combination in manganese sulfate, manganese acetate and the manganese nitrate.
5, describedly prepare anode material for lithium-ion batteries LiCo according to claim 1,2 or 4 with carbon dioxide as catalyst
xNi
yMn
zO
2Method, the concentration that it is characterized in that ammoniacal liquor in the step 2 is 0.1～0.5mol/L.
6, according to claim 5ly prepare anode material for lithium-ion batteries LiCo with carbon dioxide as catalyst
xNi
yMn
zO
2Method, it is characterized in that water temperature is 50 ℃ in the step 3.
7, describedly prepare anode material for lithium-ion batteries LiCo according to claim 1,2,4 or 6 with carbon dioxide as catalyst
xNi
yMn
zO
2Method, it is characterized in that mixing speed is 800 rev/mins in the step 3.
8, according to claim 7ly prepare anode material for lithium-ion batteries LiCo with carbon dioxide as catalyst
xNi
yMn
zO
2Method, it is characterized in that the lithium source described in the step 4 is lithium carbonate or lithium hydroxide.
9, describedly prepare anode material for lithium-ion batteries LiCo according to claim 1,2,4,6 or 8 with carbon dioxide as catalyst
xNi
yMn
zO
2Method, the material ratio that it is characterized in that ball milling in the step 4 is 10: 1.
10, according to claim 9ly prepare anode material for lithium-ion batteries LiCo with carbon dioxide as catalyst
xNi
yMn
zO
2Method, it is characterized in that sintering temperature is 850 ℃ in the step 4
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102332578A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Anode material for lithium ion battery with high power capacity and manufacturing method thereof |
| CN106953089A (en) * | 2017-05-11 | 2017-07-14 | 浙江工业职业技术学院 | A kind of method that colloidal sol flocculence prepares aluminium doping tertiary cathode material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102332578A (en) * | 2011-09-21 | 2012-01-25 | 广东达之邦新能源技术有限公司 | Anode material for lithium ion battery with high power capacity and manufacturing method thereof |
| CN106953089A (en) * | 2017-05-11 | 2017-07-14 | 浙江工业职业技术学院 | A kind of method that colloidal sol flocculence prepares aluminium doping tertiary cathode material |
| CN106953089B (en) * | 2017-05-11 | 2019-08-20 | 浙江工业职业技术学院 | A kind of method that colloidal sol flocculence prepares aluminium doping tertiary cathode material |
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