CN104282880A - Lithium-cobalt composite oxide lithium ion positive material and preparation method thereof - Google Patents
Lithium-cobalt composite oxide lithium ion positive material and preparation method thereof Download PDFInfo
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- CN104282880A CN104282880A CN201410576479.3A CN201410576479A CN104282880A CN 104282880 A CN104282880 A CN 104282880A CN 201410576479 A CN201410576479 A CN 201410576479A CN 104282880 A CN104282880 A CN 104282880A
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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
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- 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
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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Abstract
The invention provides a lithium-cobalt composite oxide lithium ion positive material and a preparation method thereof. The formula of the lithium-cobalt composite oxide lithium ion positive material provided by the invention is Li<1+y>Co<1-x>MxO2*zLi<alpha>A<v>O<beta>, wherein y is more than or equal to -0.02 and less than or equal to 0.035; x is more than or equal to 0 and less than or equal to 0.1; z is more than or equal to 0.0005 and less than or equal to 0.1; alpha is more than or equal to 0 and less than or equal to 3; (y+zalpha) is more than or equal to 0.035 and less than or equal to 0.06; beta is more than or equal to 0 and less than or equal to 5; the sum of alpha and v is equal to 2beta; A<v> is one or more of cations; and v is an average valence state of the corresponding cations. The invention further provides the preparation method of the lithium-cobalt composite oxide lithium ion positive material. The cobalt dissolving-out time is controlled to be 60-150 hours when the voltage is 4.5V; a 4.5V button battery can circulate for 50 cycles under 1C and the capacity keeping rate is 90%, even more than 95%; the cobalt dissolving-out time is controlled to be 60-100 hours when the voltage is 4.6V; a 4.6V button battery can be can circulate for 50 cycles under 1C and the capacity keeping rate is 85%, even more than 90%.
Description
Technical field
The present invention relates to a kind of lithium ion anode material and preparation method thereof, especially relate to a kind of high voltage long circulating type lithium cobalt composite oxide lithium ion anode material and preparation method thereof.
Background technology
Lithium ion battery is because of power density and energy is high, the life-span is long, is widely used in movement/information technoloy equipment and energy storage field.Lithium ion battery forms primarily of positive pole, negative pole, barrier film and electrolyte.Conventional anode material for lithium-ion batteries has cobalt acid lithium, nickle cobalt lithium manganate, LiMn2O4 and LiFePO4 etc.Cobalt acid lithium is business-like positive electrode the earliest, although poor safety performance, cost are high, the gram volume of material is high, good cycle, is therefore still most widely used positive electrode.
Along with the requirement of consumer to lithium ion battery cruising time is more and more longer, some battery manufacturers are extended working time by battery pack, and this also certainly will increase the volume of battery.With regard to cell uses, require also to increase to the energy density of material thereupon.Because the gram volume of existing negative material graphite can reach more than 350mAh/g, thus negative pole is not the bottleneck of restriction battery energy density, the positive electrode of a kind of high-energy-density of market in urgent need.
The mode improving lithium battery energy density has two kinds: 1. the compacted density improving pole piece; 2. improve the cut-ff voltage of battery charging.The positive pole of the full battery of cobalt acid lithium uses compacting generally at 4.0 ~ 4.1g/cm
3, compacting improves 0.1 g/cm
3, the energy density of battery also can have a distinct increment.The operating voltage of the full battery of cobalt acid lithium is 3.0 ~ 4.2V, and specific capacity is 145 ~ 150mAh/g, and charge cutoff voltage often improves 0.1V, and specific capacity will rise 10%.But the charge cutoff voltage improving battery can cause reducing battery safety, high-temperature storage performance and cycle performance.Be in the structural instability of high-voltage charge state cobalt acid lithium, there is cobalt stripping phenomenon in easy releasing oxygen simultaneously.Oxygen easily and inside battery electrolyte react, discharge a large amount of heats, energy accumulation is finally blasted.During high temperature, this unsteadiness aggravation, directly causes discharge capacity of the cell to reduce, also can aggravate battery explosion.In circulating battery process, due to the existence of cobalt stripping phenomenon, guiding discharge capacity reduces, and this capacitance loss is irreversible, and thus material cycle performance when high voltage uses is deteriorated.
High voltage long circulating type lithium cobalt composite oxide lithium ion anode material requires: when improving the cut-ff voltage of battery charging, positive electrode is particle surface and internal structure good stability when high potential.But in prior art, improve battery charging cut-ff voltage time, positive electrode when high potential particle surface and internal structure stability bad.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, provides a kind of high voltage macrocyclic lithium cobalt composite oxide lithium ion anode material and preparation method thereof.
The technical scheme that the present invention solves the employing of its technical problem is:
The lithium cobalt composite oxide lithium ion anode material of the present invention, its general formula is Li
1+y co
1-x m
x o
2× zLi
α a
vo
β , wherein-0.02≤
y≤ 0.035,0≤
x≤ 0.1,0.0005<
z≤ 0.1,0≤
α≤ 3,0.035≤(
y+ z
α)≤0.06,0≤
β≤ 5,
α+ v=2
β, A
vfor one or more cations, v is corresponding cationic average valence;
M is one or more in Mg, Al, Ti, Zr, Ce, Y, Ni, Mn, Si, Sc, V, Ga, Ge, Nb, Mo, In, Sn, Te, La, W, and A is one or more in Bi, Al, Ti, Zr, Y, Ni, Co, Mn, Si, Sc, V, Ga, Ge, Nb, Mo, In, Sn, Te, La, W.
Described lithium cobalt composite oxide lithium ion anode material comprises two parts: main body active part is layer structure Li
1+y co
1-x m
x o
2, Li
+there is certain concentration gradient in the radial direction of body particles, covered section consists of Li
α a
vo
β .
Described lithium cobalt composite oxide lithium ion anode material, cobalt dissolution time during 4.5V is 60h ~ 150h; Cobalt dissolution time during 4.6V controls at 60h ~ 100h.
The preparation method of the lithium cobalt composite oxide lithium ion anode material of the present invention, comprises following step:
(1) according to Li
1+y+ z
α co
1-x m
x o
2in proportioning, by cobalt source, lithium source and additive 1 dry mixed in proportion, obtain uniform mixture;
Described cobalt source is Co
3o
4, Co (OH)
2, at least one in CoOOH;
Described lithium source is Li
2cO
3, LiOH, Li
2at least one in O;
Described additive 1 is at least one in the oxide of M, hydroxide, carboxyl oxygen compound, carbonate or subcarbonate;
(2) by step (1) gained mixture in air atmosphere stove, under 850 ~ 1060 DEG C (preferably 1000 ~ 1050 DEG C), sinter 6 ~ 20h(preferably 8 ~ 10h), omnipotent pulverizing 10 ~ 30s(preferably 15 ~ 25s after cooling), the cobalt acid lithium matrix that adulterated;
(3) coated, be divided into two kinds: dry method is coated or wet method is coated;
When adopting dry method coated, the cobalt acid lithium matrix adulterated by step (2) gained and coated desired additives 2 mix, and obtain second batch mixture; Wherein the covering amount of additive 2 presses Li
1+y co
1-x m
x o
2× zLi
α a
vo
β calculate; Described additive 2 is the oxide of element A, hydroxide, alkali formula hydroxide, carbonate or subcarbonate;
When adopting wet method coated, the mass ratio of cobalt that step (2) gained has adulterated acid lithium matrix and deionized water is 1: 4 ~ 6(preferably 1: 5), the nitrate consumption of A presses Li
1+y co
1-x m
x o
2× zLi
α a
vo
β calculate; The nitrate of element A is dissolved in deionized water, adopts dispersion machine to carry out dissolving and disperse, add ammoniacal liquor adjustment pH value of solution at 6 ~ 8(preferably 7), stir 8 ~ 12 minutes, obtain hydroxide (the i.e. additive 2) suspension containing element A; Add the cobalt acid lithium matrix adulterated, continue stirring 25 ~ 35 minutes, by gained pastel in 100 ~ 120 DEG C of oven drying 8 ~ 12h, obtain second batch mixture;
(4) step (3) gained second batch mixture is sintered 5 ~ 20h (preferably 10 ~ 12h) under 100 ~ 1000 DEG C (preferably 600 ~ 950 DEG C), after 200 mesh sieves, obtain lithium cobalt composite oxide lithium ion anode material.
Matrix synthesis of the present invention adopts the mode of dry method batch mixing, obtains the radial Li of particle through heat treatment
+there is the acid of the cation doping lithium matrix of finite concentration gradient, by the region away from surface to surf zone, Li
+concentration increases gradually, and thus surface is in rich Li
+state, when selecting suitable sintering temperature and sintering time, cation doping acid lithium blapharoplast Li
+distribution and lithium source consumption closely related.Electrochemical test method (button electrical testing cobalt dissolution time) can be adopted to carry out qualitative sxemiquantitative sign.
The present invention adds and can consume Li in the cobalt acid lithium adulterated
+additive 2, through Overheating Treatment, Li
+react with additive 2 and define Li
α a
vo
β the lithium cobalt combined oxidation cobalt positive electrode Li of parcel
1+y co
1-x m
x o
2× zLi
α a
vo
β .Li in heat treatment process
+diffusion rate much larger than the transition metal ions in the acid of cation doping lithium matrix, zones of different Li
+diffusion rate and concentration and distance relevant, concentration is higher, and apart from shorter, diffusion rate is faster.
Li is consumed through additive 2
+process, Li
+redistribute and the state that tends towards stability in the acid of cation doping lithium blapharoplast inside.Different additive absorbs Li
+ability different, the thus main part Li of lithium cobalt combined oxidation cobalt positive electrode
+distribution also different, the chemical property of respective material there are differences.
Additive 2 absorbs Li
+ability not only relevant with material nature, and with heat treatment temperature and time correlation, in general, heat treatment temperature is higher, and the time is longer, inhale Li
+ability is stronger.Additive 2 absorbs Li
+can not only the structure of stable particle inside, form one deck coating layer at particle surface simultaneously.Co is completely cut off when high potential
4+with the contact of electrolyte, the surface stability of particle can be improved.
Lithium cobalt composite oxide lithium ion anode material Li
1+y co
1-x m
x o
2× zLi
α a
vo
β middle Li
+distribution and synthesis technique be closely-related.Li
+distribution directly affect again the chemical property of material.Existing chemical analysis means can not characterize Li very well
+distribution.Indirectly can adopt electrochemical test method (button electrical testing cobalt dissolution time) qualitative characterization Li
+distribution.
Cobalt stripping method of testing: the test of cobalt dissolution time adopts button cell, and be placed in 45 DEG C of thermostatic drying chambers, constant voltage charge 600h after constant current charge to certain voltage under 1C multiplying power, electric current plays peak time and is cobalt dissolution time.Because normal temperature 25 DEG C of cobalt dissolution times are oversize, therefore high temperature (45 DEG C) deterioration acceleration cobalt stripping progress is adopted to assess cobalt dissolution time.
Cobalt stripping mechanism: in constant current charge process, Li
1+y co
1-x m
x o
2× zLi
α a
vo
β in Li
+(Li is deviate from from active part
α a
vo
β middle Li
+not there is electro-chemical activity), along with Co
3+be oxidized to Co
4+, carry out constant voltage charge after charging to certain voltage, Li+ deintercalation speed is more and more less, and charging current is also more and more less.Along with the prolongation of time, be in the Co of high oxidation state
4+instability, deviates from from lattice.Now charging current sharply increases, and obvious spike appears in current versus time curve.A peak time at this peak is cobalt dissolution time.
Because commercialization cobalt acid lithium is to the requirement of energy density, high voltage type cobalt acid lithium is tending towards monocrystalline pattern, can add excessive lithium source in preparation process.Thus high voltage long circulating type lithium cobalt composite oxide lithium ion anode material adopts two-step method to synthesize usually.The first step, cobalt acid lithium matrix (monocrystalline pattern) that synthetic single crystal type cobalt dissolution time is longer, second step, suitable additive is selected to carry out coated to matrix, the present invention on this basis, first by the matrix of the high cobalt dissolution time of preparation, then absorbs Li by additive 2
+, last finished product cobalt dissolution time is controlled in suitable scope.
Material Li
1+y co
1-x m
x o
2× zLi
α a
vo
β cobalt dissolution time be by control
ycarry out regulating.The chemical formula of described lithium cobalt composite oxide is Li
1+y co
1-x m
x o
2× zLi
α a
vo
β .The chemical formula of matrix is Li
1+y+ z
α co
1-x m
x o
2.When-0.02≤(
y+ z
α) when≤0.035, matrix 4.5V cobalt dissolution time controls to control at 60h ~ 100h at 60h ~ 150h, 4.6V cobalt dissolution time; When 0.035≤(
y+ z
α)≤0.06, matrix 4.5V cobalt dissolution time controls to control at 100h ~ 250h at 150h ~ 300h, 4.6V cobalt dissolution time.
At lithium cobalt composite oxide Li
1+y co
1-x m
x o
2× zLi
α a
vo
β in, when-0.02≤
ywhen≤0.035,4.5V cobalt dissolution time controls to control at 60h ~ 100h at 60h ~ 150h, 4.6V cobalt dissolution time; When 0.035≤
y≤ 0.06,4.5V cobalt dissolution time controls to control at 100h ~ 250h at 150h ~ 300h, 4.6V cobalt dissolution time.
The synthesis technique of high voltage long circulating type lithium cobalt composite oxide comprises matrix synthesis and Surface coating.When matrix synthesizes, by matrix Li
1+y+ z
α co
1-x m
x o
2control in rich lithium state, namely 0.035≤(
y+ z
α)≤0.06.During Surface coating, by adding the additive 2 containing element A, in double sintering, absorbing lithium unnecessary in matrix, the y in body of material part is controlled :-0.02≤
y≤ 0.035.
Gained positive electrode of the present invention, cobalt dissolution time during 4.5V controls to circulate 50 weeks under 60h ~ 150h, 4.5V button cell 1C, and capability retention is 90% even more than 95%; Cobalt dissolution time during 4.6V controls to circulate 50 weeks under 60h ~ 100h, 4.6V button cell 1C, and capability retention is 85% even more than 90%.
Accompanying drawing explanation
Fig. 1 is the SEM figure of LCO-5;
Fig. 2 is the SEM figure of LCO-6;
Fig. 3 is 4.5V cycle performance curve;
Fig. 4 is 4.6V cycle performance curve;
Fig. 5 is 4.5V cobalt dissolution time curve;
Fig. 6 is 4.6V cobalt dissolution time curve.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Method of testing is described as follows.
The assembling of CR2032 type button half-cell: the mass ratio mixing of active material, PVDF and conductive black being pressed 95.5:2.3:2.2, adds NMP, stir and make slurry.Slurry is coated on aluminium foil, dry at 120 DEG C, make positive plate; CR2032 type button cell is assembled into negative pole lithium sheet, barrier film, electrolyte etc.
Cobalt dissolution time method of testing: the test of cobalt dissolution time adopts CR2032 type button half-cell, and be placed in 45 DEG C of thermostatic drying chambers, constant voltage charge 600h after constant current charge to certain voltage under 1C multiplying power, electric current plays peak time and is cobalt dissolution time.Because normal temperature 25 DEG C of cobalt dissolution times are oversize, therefore high temperature (45 DEG C, 46 DEG C) deterioration acceleration cobalt stripping progress is adopted to assess cobalt dissolution time.
CR2032 type button half-cell comes discharge capacity and the cycle performance of evaluating material.The charge-discharge performance test of battery is at room temperature carried out, the mode of first constant current constant voltage is again adopted to charge, charge cutoff voltage is the test of 4.5V(4.5V cycle performance) or the test of 4.6V(4.6V cycle performance), adopt constant-current discharge, cut-ff voltage is 3.0V, charging and discharging currents density is 1C multiplying power, circulates 50 weeks.
Embodiment 1
The lithium cobalt composite oxide lithium ion anode material of the present embodiment, its chemical formula is Li
1.034co
0.995mg
0.002al
0.002ti
0.001o
2× 0.00145LiAlO
2, there is layer structure.
Its synthetic method is:
(1) take 2000g cobaltosic oxide (~ 17 μm), 955g lithium carbonate, 2g magnesium oxide, 2.5g aluminium oxide and 2g titanium dioxide, mix, obtain uniform mixture;
(2) step (1) gained mixture is placed in air atmosphere stove, sintering temperature is 1040 DEG C, and sintering time is 10h; Gained material omnipotent pulverizing 20s after sintering after cooling, Control granularity is 17 ~ 20 μm, and gained material is numbered LCO-1; (measure its 4.5V cobalt dissolution time, 4.5V 1C discharge 50 weeks capability retentions, 4.6V cobalt dissolution time, 4.6V 1C discharge 50 weeks capability retentions, the results are shown in Table 1)
(3) get 1.67g ANN aluminium nitrate nonahydrate, add in 60g deionized water, stirring and dissolving, in solution, add ammoniacal liquor regulate the pH of solution to be 7.0, drop into 300g LCO-2, stir 30min; After being covered to complete, 120 DEG C of dry 8h, obtain second batch mixture;
(4) step (3) gained second batch mixture is sintered 10h at 650 DEG C, after coming out of the stove, cross 200 mesh sieves.Be numbered LCO-2.Measure its 4.5V cobalt dissolution time, 4.5V 1C discharge 50 weeks capability retentions, 4.6V cobalt dissolution time, 4.6V 1C discharge 50 weeks capability retentions, the results are shown in Table 1.
Embodiment 2
The lithium cobalt composite oxide lithium ion anode material of the present embodiment, its chemical formula is Li
1.034co
0.995mg
0.002al
0.002ti
0.001o
2× 0.0008Li
2tiO
3, there is layer structure.Its synthetic method is:
(1) take 2000g cobaltosic oxide (~ 17 μm), 956g lithium carbonate, 2g magnesium oxide, 2.5g aluminium oxide and 2g titanium dioxide are mixed;
(2) step (1) gained compound is placed in air atmosphere stove, at sintering temperature is 1040 DEG C, sinters 10h; Gained material omnipotent pulverizing 20s after sintering, Control granularity is 17 ~ 20 μm, obtains the cobalt acid lithium matrix adulterated; Be numbered LCO-3; Measure its 4.5V cobalt dissolution time, 4.5V 1C discharge 50 weeks capability retentions, 4.6V cobalt dissolution time, 4.6V 1C discharge 50 weeks capability retentions, the results are shown in Table 1.
(3) 1200g LCO-4 and 0.8g titanium dioxide are mixed, obtain second batch mixture;
(4) step (3) gained second batch mixture is sintered 10h in 950 DEG C, after coming out of the stove, cross 200 mesh sieves.Be numbered LCO-4.Measure its 4.5V cobalt dissolution time, 4.5V 1C discharge 50 weeks capability retentions, 4.6V cobalt dissolution time, 4.6V 1C discharge 50 weeks capability retentions, the results are shown in Table 1.
Embodiment 3
The lithium cobalt composite oxide lithium ion anode material of the present embodiment, its chemical formula is Li
1.01co
0.995mg
0.002al
0.002ti
0.001o
2× 0.02Li
2mnO
3, there is layer structure.Its synthetic method is:
(1) take 2000g cobaltosic oxide (~ 17 μm), 970g lithium carbonate, 2g magnesium oxide, 2.5g aluminium oxide and 2g titanium dioxide to mix;
(2) step (1) gained mixture is placed in air atmosphere stove, at sintering temperature is 1050 DEG C, sintering time is 10h; Gained material omnipotent pulverizing 20s after sintering after cooling, Control granularity is 17 ~ 20 μm; Be numbered LCO-5; Measure its 4.5V cobalt dissolution time, 4.5V 1C discharge 50 weeks capability retentions, 4.6V cobalt dissolution time, 4.6V 1C discharge 50 weeks capability retentions, the results are shown in Table 1;
(3) 1200gLCO-4 and 20g nanoscale manganese dioxide is mixed, obtain second batch mixture;
(4) step (3) gained second batch mixture is sintered 10h in 950 DEG C, after coming out of the stove, cross 200 mesh sieves; Obtain lithium cobalt composite oxide lithium ion anode material, be numbered LCO-6.Measure its 4.5V cobalt dissolution time, 4.5V 1C discharge 50 weeks capability retentions, 4.6V cobalt dissolution time, 4.6V 1C discharge 50 weeks capability retentions, the results are shown in Table 1.
Table 1 is each performance parameter value list of this inventive embodiments.Embodiment 1,2,3 adopts two step synthesis.Contrast coated front and coated rear each performance parameter.The cobalt dissolution time of coated rear material is shorter, and corresponding cycle performance is better.The cobalt dissolution time of rational control material effectively can improve material cycle performance under high voltages.
Illustrate: LCO-1,3,5 is respectively the matrix of embodiment 1,2,3, due to not coated, rich surface lithium, the cycle performance of 4.5V and 4.6V is poor.The too rich lithium of LCO-5, cause 4.5V and 4.6V cobalt dissolution time very long, the cycle performance of corresponding 4.5V and 4.6V is very poor.
Claims (9)
1. a lithium cobalt composite oxide lithium ion anode material, is characterized in that, its general formula is Li
1+y co
1-x m
x o
2× zLi
α a
vo
β , wherein-0.02≤
y≤ 0.035,0≤
x≤ 0.1,0.0005<
z≤ 0.1,0≤
α≤ 3,0.035≤(
y+ z
α)≤0.06,0≤
β≤ 5,
α+ v=2
β, A
vfor one or more cations, v is corresponding cationic average valence;
M is one or more in Mg, Al, Ti, Zr, Ce, Y, Ni, Mn, Si, Sc, V, Ga, Ge, Nb, Mo, In, Sn, Te, La, W, and A is one or more in Bi, Al, Ti, Zr, Y, Ni, Co, Mn, Si, Sc, V, Ga, Ge, Nb, Mo, In, Sn, Te, La, W.
2. lithium cobalt composite oxide lithium ion anode material according to claim 1, is characterized in that, cobalt dissolution time during 4.5V is 60h ~ 150h; Cobalt dissolution time during 4.6V controls at 60h ~ 100h.
3. prepare a method for lithium cobalt composite oxide lithium ion anode material as claimed in claim 1 or 2, it is characterized in that, comprise following step:
(1) according to Li
1+y+ z
α co
1-x m
x o
2in proportioning, by cobalt source, lithium source and additive 1 dry mixed in proportion, obtain uniform mixture;
Described cobalt source is Co
3o
4, Co (OH)
2, at least one in CoOOH;
Described lithium source is Li
2cO
3, LiOH, Li
2at least one in O;
Described additive 1 is at least one in the oxide of M, hydroxide, carboxyl oxygen compound, carbonate or subcarbonate;
(2) by step (1) gained mixture in air atmosphere stove, at 850 ~ 1060 DEG C, sinter 6 ~ 20h, omnipotent pulverizing 10 ~ 30s after cooling, the cobalt acid lithium matrix that adulterated;
(3) coated, be divided into two kinds: dry method is coated or wet method is coated;
When adopting dry method coated, the cobalt acid lithium matrix adulterated by step (2) gained and coated desired additives 2 mix, and obtain second batch mixture; Wherein the covering amount of additive 2 presses Li
1+y co
1-x m
x o
2× zLi
α a
vo
β calculate; Described additive 2 is the oxide of element A, hydroxide, alkali formula hydroxide, carbonate or subcarbonate;
When adopting wet method coated, the cobalt acid lithium matrix that step (2) gained has adulterated and the mass ratio of deionized water are that the nitrate consumption of 1: 4 ~ 6, A presses Li
1+y co
1-x m
x o
2× zLi
α a
vo
β calculate; The nitrate of element A is dissolved in deionized water, adopts dispersion machine to carry out dissolving and disperseing, add ammoniacal liquor and regulate pH value of solution 6 ~ 8, stir 8 ~ 12 minutes, obtain the hydroxide suspension liquid containing element A; Add the cobalt acid lithium matrix adulterated, continue stirring 25 ~ 35 minutes, by gained pastel in 100 ~ 120 DEG C of oven drying 8 ~ 12h, obtain second batch mixture;
(4) step (3) gained second batch mixture is sintered 5 ~ 20h at 100 ~ 1000 DEG C, after 200 mesh sieves, obtain lithium cobalt composite oxide lithium ion anode material.
4. the method preparing lithium cobalt composite oxide lithium ion anode material according to claim 3, is characterized in that, in step (2), the temperature of sintering is 1000 ~ 1050 DEG C.
5. the method preparing lithium cobalt composite oxide lithium ion anode material according to claim 3 or 4, is characterized in that, in step (2), the time of sintering is 8 ~ 10h.
6. the method preparing lithium cobalt composite oxide lithium ion anode material according to claim 3 or 4, is characterized in that, in step (2), the time of omnipotent pulverizing is 15 ~ 25s.
7. the method preparing lithium cobalt composite oxide lithium ion anode material according to claim 3 or 4, is characterized in that, in step (3), when adopting wet method coated, the cobalt acid lithium matrix adulterated and the mass ratio of deionized water are 1: 5.
8. the method preparing lithium cobalt composite oxide lithium ion anode material according to claim 3 or 4, is characterized in that, in step (4), the temperature of sintering is 600 ~ 950 DEG C.
9. the method preparing lithium cobalt composite oxide lithium ion anode material according to claim 3 or 4, is characterized in that, in step (4), the time of sintering is 10 ~ 12h.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104953096A (en) * | 2015-05-06 | 2015-09-30 | 湖南杉杉新能源有限公司 | Surface-modified high-voltage lithium cobalt oxide positive material and preparation method thereof |
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| CN104953096A (en) * | 2015-05-06 | 2015-09-30 | 湖南杉杉新能源有限公司 | Surface-modified high-voltage lithium cobalt oxide positive material and preparation method thereof |
| CN104953096B (en) * | 2015-05-06 | 2017-07-14 | 湖南杉杉新能源有限公司 | High voltage lithium cobalt oxide anode that a kind of surface is modified and preparation method thereof |
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| CN107251286B (en) * | 2015-12-23 | 2020-05-22 | 株式会社Lg 化学 | Positive electrode active material for secondary battery and secondary battery comprising same |
| CN107293703A (en) * | 2016-04-12 | 2017-10-24 | 河南科隆新能源股份有限公司 | A kind of modified tertiary cathode material and preparation method thereof |
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| WO2017206633A1 (en) * | 2016-06-01 | 2017-12-07 | 湖南杉杉能源科技股份有限公司 | High rate lithium cobalt oxide positive electrode material and manufacturing method thereof |
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| KR20190016963A (en) * | 2016-06-01 | 2019-02-19 | 후난 산산 에너지 테크놀로지 컴퍼니 리미티드 | High rate lithium cobalt oxide cathode material and manufacturing method thereof |
| WO2018107545A1 (en) * | 2016-12-14 | 2018-06-21 | 先雪峰 | Lithium ion battery composite active substance and preparation method therefor, lithium ion battery electrode slurry, cathode or anode, and lithium ion battery |
| CN106450337A (en) * | 2016-12-14 | 2017-02-22 | 先雪峰 | Application of additive, electrode slurry, additive slurry, positive electrode or negative electrode of lithium ion battery, preparation method of positive electrode or negative electrode of lithium ion battery, and lithium ion battery |
| CN109997255A (en) * | 2017-10-31 | 2019-07-09 | 蔚山科学技术院 | Active material for anode of secondary cell, preparation method and the secondary cell containing it |
| CN111029535A (en) * | 2018-10-09 | 2020-04-17 | 北大先行科技产业有限公司 | Composite positive electrode material of lithium ion battery and preparation method thereof |
| CN111081987A (en) * | 2018-10-18 | 2020-04-28 | 湖南杉杉能源科技股份有限公司 | Lithium cobaltate cathode material of lithium ion battery with voltage of more than 4.45V and preparation method thereof |
| CN115676902A (en) * | 2021-07-28 | 2023-02-03 | 天津国安盟固利新材料科技股份有限公司 | Al gradient type lithium cobaltate-doped positive electrode material and preparation method thereof |
| CN115676902B (en) * | 2021-07-28 | 2024-05-28 | 天津国安盟固利新材料科技股份有限公司 | Al gradient doped lithium cobalt oxide positive electrode material and preparation method thereof |
| CN115986107A (en) * | 2022-12-12 | 2023-04-18 | 广东邦普循环科技有限公司 | Lithium cobaltate cathode material and preparation method thereof |
| CN115986107B (en) * | 2022-12-12 | 2024-03-12 | 广东邦普循环科技有限公司 | Lithium cobalt oxide positive electrode material and preparation method thereof |
| CN115924994A (en) * | 2022-12-27 | 2023-04-07 | 蜂巢能源科技股份有限公司 | Ternary cathode material and preparation method and application thereof |
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