CN100495770C - Lithiumion secondary battery anode material LixCoyLazMn(z-y-z) O4 and producing process thereof - Google Patents
Lithiumion secondary battery anode material LixCoyLazMn(z-y-z) O4 and producing process thereof Download PDFInfo
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- CN100495770C CN100495770C CNB2007100569440A CN200710056944A CN100495770C CN 100495770 C CN100495770 C CN 100495770C CN B2007100569440 A CNB2007100569440 A CN B2007100569440A CN 200710056944 A CN200710056944 A CN 200710056944A CN 100495770 C CN100495770 C CN 100495770C
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Abstract
This invention relates to a positive material of Li ionic secondary cells with a spinel structure and its preparation method characterizing that the chemical formula is LixCoyLazMn(2-y-z)O4, and x=0.98-1.05, y=0.01-0.10, z=0.005-0.02. The preparation method includes the following steps: 1, preparing soluble Mn salt solution to spherical MnCO3 with a precipitator NH4HCO3 or (NH4)2CO3, 2, covering the MnCO3 with CoCO3 and La2(CO3)3, 3, baking the covered MnCO3 under high temperature to get Mn3O4 powder doped with Co and La, 4, mixing the doped Mn3O4 powder with Li2CO3, 5, baking, 6, crushing and screening, which prepares LiMn2O4 positive material uniformly doped with Co and La to increase the circulation performance of the Li ionic cells, stabilize and keep the volume of cells.
Description
Technical field
The present invention relates to the lithium ion secondary battery anode material field, relate in particular to a kind of lithium ion secondary battery anode material Li
xCo
yLa
zMn
(2-y-z)O
4And preparation method thereof.
Background technology
Along with the fast development of modern information technologies, portable type electronic products such as mobile phone, notebook computer and digital camera are strong day by day to the demand of the battery of high performance-price ratio.Lithium rechargeable battery has obtained in the portable electronics field using widely owing to have advantages such as energy density height, memory-less effect.The selection of positive electrode is depended in the research and development of the lithium rechargeable battery of high-performance and low-cost, key.Lithium ion secondary battery anode material LiCoO commonly used at present
2Cost an arm and a leg and certain toxicity is arranged, and positive electrode LiMn
2O
4Have then that price is low, aboundresources, the environment amenable characteristics of nontoxic pollution-free, the lithium ion secondary battery anode material that is considered to have wide application prospects.But LiMn in actual applications,
2O
4Still there is certain defective, LiMn
2O
4Cycle performance poor, particularly under the high temperature capacity decline fall fast.This mainly is because with LiMn through a large amount of studies confirm that
2O
4In the lithium rechargeable battery as positive electrode, positive electrode is immersed in the electrolyte, and manganese ion dissolves in electrolyte and causes due to the material structure destruction, and this destruction is at high temperature more serious.At this defective, existing solution is by mechanical means, promptly passes through methods such as stirring, ball milling at LiMn under solid-state
2O
4Mix in the material other metallic element, for example cobalt, aluminium, magnesium, nickel wait and improve LiMn
2O
4The stability of frame structure, prevent the dissolving of manganese ion, reduce the variation of its structure in the battery charge and discharge process, improve its cycle performance.From application practice, this mechanical means does not reach the purpose of even doping, the phenomenon that manganese ion dissolves still can occur in the sparse part of doped metallic elements, thereby LiMn
2O
4Cycle performance still do not have be improved significantly.In addition, show, at LiMn through practice
2O
4The cobalt that mixes in the structure, though the cycle performance of battery is improved, but it is more to cause battery capacity to descend, and has reduced battery performance.
Summary of the invention
Main purpose of the present invention is to provide a kind of Stability Analysis of Structures, charge-discharge performance is good and specific capacity is high lithium ion secondary battery anode material and preparation method thereof at the problems referred to above.This material is the even doping Co with spinel structure, the LiMn of La
2O
4, its preparation method is at first by crystallization control method synthesizing spherical MnCO
3, at its complete one deck Co, La compound of coating equably in surface, the product after the coating mixes with lithium compound after high-temperature roasting, prepares the LiMn of doping Co, La then by pyroreaction with the crystallization control method in continuation then
2O
4Powder is subsequently by the product of pulverizing, classification needing to obtain particle diameter.
The present invention solves the concrete technical scheme that its technical problem adopts:
A kind of lithium ion secondary battery anode material is characterized in that its chemical formula is:
Li
xCo
yLa
zMn
(2-y-z)O
4X=0.98～1.05 wherein, y=0.01～0.10, z=0.005～0.02 has spinel structure.
The preparation method of above-mentioned lithium ion secondary battery anode material is characterized in that comprising the steps:
1). with concentration is the precipitation reagent NH that the solvable manganese salt solution concentration of 1～4mol/L is 1～3mol/L
4HCO
3Or (NH
4)
2CO
3Solution precipitates the spherical MnCO of preparation
3, the pH value during the control precipitation is 7～10, and reaction temperature is 10～50 ℃, and solvable manganese salt solution addition hourly is 1%～6% of a reactor volume, and the outermost linear velocity of paddle is 2～5m/s, makes MnCO
3Granularity is controlled at 5～20 μ m;
2). after solvable manganese salt solution all adds and reacts, to sediment MnCO
3Coat CoCO
3And La
2(CO
3)
3, adding concentration in reactor simultaneously is the solvable cobalt salt solution of 1～2mol/L and the solvable lanthanum salting liquid that concentration is 1～2mol/L, and continuation adding concentration is the precipitation reagent NH of 1～3mol/L
4HCO
3Or (NH
4)
2CO
3Solution, Co, La, the atomic ratio of Mn is: Co/La/Mn=y/z/ (2-y-z), y=0.01～0.10 wherein, z=0.005～0.02, pH value during the control precipitation is 7～10, reaction temperature is 10～50 ℃, and cobalt salt and lanthanum salting liquid addition hourly are 1%～6% of reactor volume, and the outermost linear velocity of paddle is 2～5m/s;
3). will coat CoCO
3And La
2(CO
3)
3After MnCO
3At 1000～1250 ℃ roasting temperature, be incubated 6～12 hours; Obtaining main body after the roasting is the Mn of doping Co, La
3O
4Powder is pulverized and 200 mesh sieves are standby excessively;
4). the doping Co that will pulverize, the Mn of La
3O
4Powder and granularity are the Li of 5～20 μ m
2CO
3Mix, mixed proportion is with atomic ratio measuring: Li/ (Mn+Co+La)=0.490～0.525;
5). mixed powder is packed into and is carried out roasting in the saggar, at first is incubated 2～10 hours under 400～600 ℃ of temperature, is incubated 6～24 hours then under 700～850 ℃ of temperature, and to send into air capacity be 0.5～2L/h to the per kilogram material during roasting;
6). cross 200 mesh sieves after the material after the roasting is pulverized and obtain Li
xCo
yLa
zMn
(2-y-z)O
4Powder, forming a kind of pattern with spinel structure is that class sphere, specific area are less than 2m
2The crystallite aggregate of/g, granularity D50=5～30 μ m.
Described solvable manganese salt is MnSO
4Or Mn (NO
3)
2Described solvable cobalt salt is CoSO
4, Co (NO
3)
2Or CoCl
2Described solvable lanthanum salt is La
2(SO
4)
3, La (NO
3)
3Or LaCl
3
Described step 2). in NH
4HCO
3Or (NH
4)
2CO
3The excessive adding 5%～10% of solution is to guarantee that reactant all precipitates.
Above-mentioned MnCO
3The crystallization control method is adopted in the preparation of powder, by to the concentration of manganese salt solution and precipitation reagent and adding speed, reactor rotating speed, pH value of solution value, the isoparametric Comprehensive Control of temperature, guarantees the MnCO that generates
3Be controlled at the spheric granules of 5～20 μ m for granularity.Above-mentioned coating CoCO
3And La
2(CO
3)
3Process is the coating process of crystallization control, makes CoCO by parameters such as the control concentration of cobalt salt solution, lanthanum salting liquid and precipitation reagent and adding speed, reactor rotating speed, pH value of solution value, temperature
3And La
2(CO
3)
3At MnCO
3Crystallization slowly, growth on the particle, thus realize whole M nCO
3The even doping of particle surface.MnCO after the coating
3Powder mainly contains two purposes at 1000～1250 ℃ roasting temperature, and one is the drying materials with the wet method reaction, and another is to remove remaining anion such as sulfate radical by high temperature.Then roasting time is short to select the temperature height, selects temperature to hang down and then needs corresponding lengthening roasting time.
The invention has the beneficial effects as follows:
Lithium ion secondary battery anode material Li provided by the invention
xCo
yLa
zMn
(2-y-z)O
4And preparation method thereof, it is characterized by at spherical MnCO
3Method by crystallization control on the particle coats CoCO
3And La
2(CO
3)
3, make CoCO
3And La
2(CO
3)
3At MnCO
3Crystallization slowly, growth on the particle, thus realize whole M nCO
3The even doping of particle surface, rather than at follow-up Mn
3O
4With Li
2CO
3Mode by mechanical mixture in the process of mixing adds, and therefore can form evenly complete coating layer, effectively prevents to be immersed in the dissolving of manganese ion in the positive electrode in the electrolyte, and the cycle performance of lithium rechargeable battery is improved.Because therefore these positive electrode while mixing and doping cobalt and two kinds of elements of lanthanum not only improve the lithium battery cycle performance, also play effect stable and that keep battery capacity again.
Description of drawings
Fig. 1 is the pattern (SEM) of positive electrode under electron microscope of embodiment 1 preparation;
Fig. 2 is the thing phase (XRD) of the positive electrode of embodiment 1 preparation.
Below in conjunction with embodiment to the detailed description of the invention.
Embodiment
Embodiment 1
A kind of lithium ion secondary battery anode material, its chemical formula is:
Li
xCo
yLa
zMn
(2-y-z)O
4, x=1.0 wherein, y=0.05, z=0.01 has spinel structure.
The preparation method of above-mentioned lithium ion secondary battery anode material comprises the steps:
1). with concentration is the MnSO of 2mol/L
4Solution 10L concentration is the precipitation reagent NH of 1.5mol/L
4HCO
3Solution 26.7L precipitates, and is equipped with spherical MnCO with the crystallization control legal system
3, reaction temperature is 10～50 ℃, the pH value during the control precipitation is 8～9, by NH
4HCO
3The addition control pH value of solution, the reactor volume that adopts in this example is 100L, MnSO
4The addition of solution is 1～6L/h, and the outermost linear velocity of paddle is 3.5m/s, makes MnCO
3Granularity is controlled at 5～20 μ m;
2). work as MnSO
4After whole addings of solution and the reaction, to sediment MnCO
3Coat CoCO
3And La
2(CO
3)
3, in reactor, add the CoSO that concentration is 1.5mol/L simultaneously
4Solution 0.343L and concentration are the La of 1.5mol/L
2(SO
4)
3Solution 0.034L, and continuation adding concentration is the precipitation reagent NH of 1.5mol/L
4HCO
3Solution 1.07L, last excessive adding NH
4HCO
3Solution 2.6L is to guarantee that reactant all precipitates.Co, La, the atomic ratio of Mn is: Co/La/Mn=0.05/0.01/1.94, reaction temperature is 10～50 ℃, the pH value during the control precipitation is 8～9, by NH
4HCO
3The addition control pH value of solution, CoCO
3And La
2(CO
3)
3The addition of solution is respectively 1～6L/h, and the outermost linear velocity of paddle is 3.5m/s;
3). will coat CoCO
3And La
2(CO
3)
3After MnCO
3At 1050 ℃ roasting temperature, be incubated 8 hours; Obtaining main body after the roasting is the Mn of doping Co, La
3O
4Powder is pulverized and 200 mesh sieves are standby excessively;
4). the doping Co that will pulverize, the Mn of La
3O
4Powder 1.535Kg and granularity are the Li of 5-20 μ m
2CO
3Powder 0.369Kg mixes, and its atomic ratio is: Li/ (Mn+Co+La)=0.50;
5). mixed powder is packed into and is carried out roasting in the saggar, at first insulation 6 hours under 600 ℃ of temperature, insulation 16 hours under 800 ℃ of temperature then, to send into air capacity be 0.5～2L/h to the per kilogram material during roasting;
6). cross 200 mesh sieves after the material after the roasting is pulverized and obtain Li
xCo
yLa
zMn
(2-y-z)O
4Powder, x=1.0 wherein, y=0.05, z=0.01, forming a kind of pattern with spinel structure is that class sphere, specific area are less than 2m
2The crystallite aggregate of/g, granularity D50=5～30 μ m.
In above-mentioned steps 5). roasting process in, programming rate is 4～10 ℃/min, cooling rate is 1 ℃/min to 600 ℃, cools off with stove below 600 ℃.
Fig. 1 is the pattern (SEM) of positive electrode under electron microscope of present embodiment preparation, and as seen from the figure, the particle of reunion is the class sphere; Fig. 2 is the thing phase (XRD) of the positive electrode of present embodiment preparation.Can draw this material by figure is spinel structure.
A kind of lithium ion secondary battery anode material, its chemical formula is:
Li
xCo
yLa
zMn
(2-y-z)O
4, x=1.0 wherein, y=0.05, z=0.005 has spinel structure.Its preparation process and embodiment 1 ratio change step 1). and the pH value when middle control precipitates is 7～8, and the outermost linear velocity of paddle is 2m/s; Change step 2). middle CoSO
4Solution concentration is 1.5mol/L, and consumption is 0.343L, La
2(SO
4)
3Solution concentration is 0.017L for the 1.5mol/L consumption, MnCO
3Coat CoCO
3And La
2(CO
3)
3The proportioning of afterproduct is: Co/La/Mn=0.05/0.005/1.945, and the pH value during the control precipitation is 7～8, the outermost linear velocity of paddle is 2m/s.Change step 4). the doping Co that will pulverize, the Mn of La
3O
4Powder 1.532Kg and granularity are the Li of 5～20 μ m
2CO
3Powder 0.369Kg mixes, and its atomic ratio is: Li/ (Mn+Co+La)=0.50.Other is with embodiment 1.
Embodiment 3
A kind of lithium ion secondary battery anode material, its chemical formula is:
Li
xCo
yLa
zMn
(2-y-z)O
4, x=1.0 wherein, y=0.05, z=0.02 has spinel structure.Its preparation process and embodiment 1 relatively change step 1). and the pH value when middle control precipitates is 9～10, and the outermost linear velocity of paddle is 5m/s.Change step 2). middle CoSO
4Solution concentration is 1.5mol/L, and consumption is 0.345L, La
2(SO
4)
3Solution concentration is 0.069L for the 1.5mol/L consumption, MnCO
3Coat CoCO
3And La
2(CO
3)
3The proportioning of afterproduct is: Co/La/Mn=0.05/0.02/1.93, and the pH value during the control precipitation is 9～10, the outermost linear velocity of paddle is 5m/s.Change step 4). the doping Co that will pulverize, the Mn of La
3O
4Powder 1.543Kg and granularity are the Li of 5～20 μ m
2CO
3Powder 0.369Kg mixes, and its atomic ratio is: Li/ (Mn+Co+La)=0.50.Other is with embodiment 1.
Embodiment 4
A kind of lithium ion secondary battery anode material, its chemical formula is:
Li
xCo
yLa
zMn
(2-y-z)O
4, x=1.0 wherein, y=0.01, z=0.01 has spinel structure.Its preparation process and embodiment 1 relatively change step 2). middle CoSO
4Solution concentration is 1.5mol/L, and consumption is 0.067L, La
2(SO
4)
3Solution concentration is 0.034L for the 1.5mol/L consumption, MnCO
3Coat CoCO
3And La
2(CO
3)
3The proportioning of afterproduct is: Co/La/Mn=0.01/0.01/1.98.Change step 4). the doping Co that will pulverize, the Mn of La
3O
4Powder 1.534Kg and granularity are the Li of 5～20 μ m
2CO
3Powder 0.369Kg mixes, and its atomic ratio is: Li/ (Mn+Co+La)=0.50.Other is with embodiment 1.
Embodiment 5
A kind of lithium ion secondary battery anode material, its chemical formula is:
Li
xCo
yLa
zMn
(2-y-z)O
4, x=1.0 wherein, y=0.1, z=0.01 has spinel structure.Its preparation process and embodiment 1 relatively change step 2). middle CoSO
4Solution concentration is 1.5mol/L, and consumption is 0.705L, La
2(SO
4)
3Solution concentration is 0.035L for the 1.5mol/L consumption, MnCO
3Coat CoCO
3And La
2(CO
3)
3The proportioning of afterproduct is: Co/La/Mn=0.1/0.01/1.89.Change step 4). the doping Co that will pulverize, the Mn of La
3O
4Powder 1.536Kg and granularity are the Li of 5～20 μ m
2CO
3Powder 0.369Kg mixes, and its atomic ratio is: Li/ (Mn+Co+La)=0.50.Other is with embodiment 1.
Embodiment 6
A kind of lithium ion secondary battery anode material, its chemical formula is:
Li
xCo
yLa
zMn
(2-y-z)O
4, x=0.98 wherein, y=0.05, z=0.01 has spinel structure.
Its preparation process changes step 4). the Mn of middle doping Co, La
3O
4Powder 1.535Kg and Li
2CO
3Powder 0.362Kg mixes, and its atomic ratio is: Li/ (Mn+Co+La)=0.49, other is with embodiment 1.
Embodiment 7
A kind of lithium ion secondary battery anode material, its chemical formula is:
Li
xCo
yLa
zMn
(2-y-z)O
4, x=1.05 wherein, y=0.05, z=0.01 has spinel structure.
Its preparation process changes step 4). the Mn of middle doping Co, La
3O
4Powder 1.536Kg and Li
2CO
3Powder 0.388Kg mixes, and its atomic ratio is: Li/ (Mn+Co+La)=0.525, other is with embodiment 1.
Embodiment 8
Change step 5). in the roasting time of mixed powder, at first insulation 10 hours under 400 ℃ of temperature, insulation 24 hours under 700 ℃ of temperature then, other is with embodiment 1.
Embodiment 9
Change step 5). in the roasting time of mixed powder, at first insulation 8 hours under 500 ℃ of temperature, insulation 12 hours under 850 ℃ of temperature then, other is with embodiment 1.
Change step 3). in will coat CoCO
3And La
2(CO
3)
3After MnCO
3At 1250 ℃ roasting temperature, be incubated 6 hours, other is with embodiment 1.
Embodiment 11
Change step 3). in will coat CoCO
3And La
2(CO
3)
3After MnCO
3At 1000 ℃ roasting temperature, be incubated 12 hours, other is with embodiment 1.
The mechanical mixture of Comparative Examples 1 doping Co
With Mn
3O
41.487Kg, Li
2CO
30.369Kg, Co
3O
40.040Kg, (Li/Mn/Co=1.0/1.95/0.05) mechanical mixture, mixed material was handled 16 hours down at 800 ℃, obtained comparative sample after pulverizing, sieving.
The crystallisation preparation of Comparative Examples 2 doping Co
Its chemical formula is LiCo
xMn
(2-x)O
4, wherein x=0.05 has spinel structure.Its preparation process and embodiment 1 relatively change step 2) middle CoSO
4Solution concentration is 1.5mol/L, and consumption is 0.342L, MnCO
3Coat CoCO
3The proportioning of afterproduct is: Co/Mn=0.05/1.95.Change the Mn of doping Co in the step 4)
3O
4Powder 1.527Kg and Li
2CO
3Powder 0.369Kg mixes, and its atomic ratio is: Li/ (Mn+Co)=0.50. other with embodiment 1.
The electric performance test result with the lithium ion secondary battery anode material that makes in the foregoing description has been listed in cycle performance test in the table 1.Cell positive material consists of: 90% positive active material+5% conductive carbon black+5%PVDF; Battery cathode is pure lithium; Electrolyte is 1mol LiPF
61:1EC+DEC; Barrier film is the Cellgard2400 micro-pore septum.Voltage range is 3.0-4.3V, and charge-discharge magnification is 0.5C.The charging/discharging apparatus that uses discharges and recharges instrument for blue electricity.
Data are as can be seen from table 1:
1) positive electrode produced of its cycle performance of positive electrode of the present invention that makes with the crystallization control method and mechanical mixture method relatively is improved.
2) Li that obtains by while mixing and doping Co, La
xCo
yLa
zMn
(2-y-z)O
4LiMn than the Co that only mixes
2O
4The height of discharge capacity first.
Table 1 cycle performance test chart
Claims (3)
1, a kind of preparation method of lithium ion secondary battery anode material, the chemical formula of described lithium ion secondary battery anode material is: Li
xCo
yLa
zMn
(2-y-z)O
4, x=0.98～1.05 wherein, y=0.01～0.10, z=0.005～0.02 has spinel structure; It is characterized in that comprising the steps:
1) with concentration is the precipitation reagent NH that the solvable manganese salt solution concentration of 1～4mol/L is 1～3mol/L
4HCO
3Or (NH
4)
2CO
3Solution precipitates the spherical MnCO of preparation
3, the pH value during the control precipitation is 7～10, and reaction temperature is 10～50 ℃, and solvable manganese salt solution addition hourly is 1%～6% of a reactor volume, and the outermost linear velocity of paddle is 2～5m/s, makes MnCO
3Granularity is controlled at 5～20 μ m;
2) after solvable manganese salt solution all adds and reacts, to sediment MnCO
3Coat CoCO
3And La
2(CO
3)
3, adding concentration in reactor simultaneously is the solvable cobalt salt solution of 1～2mol/L and the solvable lanthanum salting liquid that concentration is 1～2mol/L, and continuation adding concentration is the precipitation reagent NH of 1～3mol/L
4HCO
3Or (NH
4)
2CO
3Solution, Co, La, the atomic ratio of Mn is: Co/La/Mn=y/z/ (2-y-z), y=0.01～0.10 wherein, z=0.005～0.02, pH value during the control precipitation is 7～10, reaction temperature is 10～50 ℃, and cobalt salt and lanthanum salting liquid addition hourly are 1%～6% of reactor volume, and the outermost linear velocity of paddle is 2～5m/s;
3) will coat CoCO
3And La
2(CO
3)
3After MnCO
3At 1000～1250 ℃ roasting temperature, be incubated 6～12 hours; Obtaining main body after the roasting is the Mn of doping Co, La
3O
4Powder is pulverized and 200 mesh sieves are standby excessively;
The doping Co that 4) will pulverize, the Mn of La
3O
4Powder and granularity are the Li of 5-20 μ m
2CO
3Mix, mixed proportion is with atomic ratio measuring: Li/ (Mn+Co+La)=0.490～0.525;
5) mixed powder is packed into and is carried out roasting in the saggar, at first is incubated 2～10 hours under 400～600 ℃ of temperature, is incubated 6～24 hours then under 700～850 ℃ of temperature, and to send into air capacity be 0.5～2L/h to the per kilogram material during roasting;
6) cross 200 mesh sieves after the material after the roasting is pulverized and obtain Li
xCo
yLa
zMn
(2-y-z)O
4Powder, forming a kind of pattern with spinel structure is that class sphere, specific area are less than 2m
2The crystallite aggregate of/g, granularity D50=5～30 μ m.
2, the preparation method of lithium ion secondary battery anode material according to claim 1 is characterized in that described solvable manganese salt is MnSO
4Or Mn (N0
3)
2Described solvable cobalt salt is CoSO
4, Co (NO
3)
2Or CoCl
2Described solvable lanthanum salt is La
2(SO
4)
3, La (NO
3)
3Or LaCl
3
3, the preparation method of lithium ion secondary battery anode material according to claim 1 is characterized in that described step 2) in NH
4HCO
3Or (NH
4)
2CO
3The excessive adding 5%～10% of solution is to guarantee that reactant all precipitates.
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| CN102195042A (en) * | 2010-03-09 | 2011-09-21 | 中国科学院过程工程研究所 | High performance lithium ion battery anode material lithium manganate and preparation method thereof |
| CN101859894A (en) * | 2010-05-19 | 2010-10-13 | 青岛华冠恒远锂电科技有限公司 | Method for synthesizing lithium ion battery anode material of LiMn2-xMxO4(x is 0.01-0.2) at high pressure |
| CN102324516B (en) * | 2011-10-09 | 2014-03-12 | 湖南化工研究院 | Preparation method of lithium manganate precursor as lithium ion battery anode material |
| KR102014983B1 (en) | 2011-11-18 | 2019-08-28 | 삼성전자주식회사 | Cathode and lithium battery using same |
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