CN102437323A - Anode material of lithium ion battery and preparation method thereof - Google Patents
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Abstract
The invention relates to an anode material of a lithium ion battery and a preparation method thereof. The preparation method is characterized by adopting the following processing steps that: (1) lithium salt, manganese salt, nickel salt, cobalt salt and M salt are dissolved in deionized water in a stirring condition, a complexing agent is added into the deionized water, and the pH value is regulated; (2) a mixed solution obtained in the step (1) is evaporated at a constant temperature, and sol is obtained; (3) the sol is dried, and xerogel is obtained; (4) the xerogel is calcined, and a precursor is obtained; and (5) the precursor is ground after being cooled to a room temperature, the ground precursor is calcined, and the anode material Li[LiaMnbNicCodMe]O2 of the lithium ion battery is obtained after the ground precursor is cooled to a room temperature. The anode material of the lithium ion battery, which is synthesized by adopting the preparation method, has low cobalt content, so the pollution to the environment is decreased while the production cost is reduced; and the anode material synthesized after being compacted has the advantages of high specific capacity, good cycle performance, simple process, low cost, and the like.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof, belong to technical field of lithium ion.
Background technology
Demand along with energy storage fields such as the rise of the extensive use of portable mobile electronic product and pure EHV electric and hybrid vehicle and wind energy, solar energy presses for the lithium ion battery of developing height ratio capacity, low production cost.In lithium ion battery, the performance of positive electrode and cost play decisive role again to the overall performance and the price of lithium battery.Therefore, the anode material for lithium-ion batteries of exploitation high-performance and low production cost becomes the key point that improves the lithium ion battery performance.Present stage, commercial anode material for lithium-ion batteries mainly contained LiCoO
2, LiMn
2O
4, LiFePO
4, and LiCo
1/3Mn
1/3Ni
1/3O
2Deng.Spinel-type LiMn
2O
4Theoretical capacity is 148mAh/g, and about the about 120mAh/g of actual discharge capacity, the while because of the Jahn-Teller distortion effect causes capacity attenuation very fast, has restricted this Development of Materials to a certain extent under hot environment.Stratiform LiCoO
2Theoretical specific capacity is about 274mAh/g, and reality high-volume capacity can reach about 130～150mAh/g, and the price of Co is higher and have toxicity, and this material will progressively be substituted.Stratiform LiCo
1/3Mn
1/3Ni
1/3O
2Theoretical specific capacity is about 278mAh/g, and reality high-volume capacity can reach 190～200mAh/g.LiFePO
4Theoretical specific capacity is about 170mAh/g, and reality high-volume capacity can reach about 160mAh/g; But this material preparation condition harshness and cryogenic property are bad, and theoretical capacity is not high, but room for promotion is very limited.The lithium-rich anode material of high power capacity and stable circulation causes extensive concern in recent years, and lithium-rich anode material mainly is Li
2MnO
3With stratified material LiMO
2The solid solution that (M is Ni, Co, Fe or Cr) forms has α-NaFeO
2Layer structure.
At present in existing report, the method for synthetic lithium-rich anode material is more with coprecipitation, but coprecipitation complex process in process of production, it is more to consume raw material, should not produce in batches as large-scale industrialization.
Summary of the invention
The objective of the invention is to overcome the deficiency that exists in the prior art, a kind of anode material for lithium-ion batteries and preparation method thereof is provided, this anode material for lithium-ion batteries has height ratio capacity, good cycle.
According to technical scheme provided by the invention, said anode material for lithium-ion batteries, characteristic is: the chemical general formula of said positive electrode is Li [Li
aMn
bNi
cCo
dM
e] O
2, wherein 0.05≤a≤0.25,0.4≤b≤0.8,0.03≤c, d, e≤0.15, and a+b+c+d+e=1, M is one or more among Al, Cr, Ti, the Mg.
The present invention also protects a kind of preparation method of anode material for lithium-ion batteries, and characteristic is to adopt following processing step:
(1) lithium salts, manganese salt, nickel salt, cobalt salt and M salt are dissolved in the deionized water under stirring condition, the total concentration of lithium salts, manganese salt, nickel salt, cobalt salt and M salt is 0.2～6mol/L, and mixing speed is 90～180 rev/mins, and mixing time is 10～60 minutes; Add the complexing agent aqueous solution that concentration is 0.5～3mol/L again, low whipping speed is that to drip mass percentage concentration under 90～180 rev/mins the condition be that to regulate the pH value be 6～8 for 15～28% ammonia spirit again; The mol ratio of said lithium salts, manganese salt, nickel salt, cobalt salt and M salt is 1～1.25: 0.4～0.8: 0.03～0.15: 0.03～0.15: 0.03～0.15, and M salt is one or more in aluminium salt, chromic salts, titanium salt, the magnesium salts; The total amount of said manganese salt, nickel salt, cobalt salt and M salt and the mol ratio of complexing agent are 1: 0.9～1.2;
(2) under 50～90 ℃ condition, carried out evaporation at constant temperature 4～10 hours under the condition that the mixed solution low whipping speed that step (1) is obtained is 200～500 rev/mins, obtain colloidal sol;
(3) colloidal sol is placed air dry oven under 80～180 ℃ of conditions dry 4～12 hours, drive away moisture, obtain xerogel with evaporation;
(4) place Muffle furnace to calcine xerogel, programming rate is 1～5 ℃/min, is warming up to 200～600 ℃, calcines 2～20 hours, obtains presoma;
(5) presoma is cooled to after the room temperature grinding in ball grinder 0.5～2 hour; Presoma compacting after grinding is placed in the Muffle furnace; In excess oxygen or air atmosphere under calcine, programming rate is 3～8 ℃/min, is warming up to 700～1100 ℃; Calcined 3～30 hours, and promptly obtained described anode material for lithium-ion batteries Li [Li after being cooled to room temperature
aMn
bNi
cCo
dM
e] O
2
Said lithium salts is one or more in lithium carbonate, lithium nitrate, lithium acetate, the lithium hydroxide; Said manganese salt is one or more in manganese sulfate, manganese nitrate, the manganese acetate; Said nickel salt is one or more in nickelous sulfate, nickel nitrate, the nickel acetate; Said cobalt salt is one or more in cobaltous sulfate, cobalt nitrate, the cobalt acetate; Said aluminium salt is one or more in aluminum sulfate, aluminum nitrate and the lithium acetate; Said chromic salts is one or more in chromium sulfate, chromic nitrate and the chromium acetate; Said titanium salt is one or more in titanium sulfate, Titanium Nitrate, the acetate titanium; Said magnesium salts is one or more in magnesium nitrate, magnesium sulfate, the magnesium acetate.
Said complexing agent aqueous solution is one or more the aqueous solution in citric acid, tartaric acid, the ethylene glycol.
In the step (5), said excess oxygen is that oxygen concentration is greater than 21%.
The pH value is adjusted to 7 for neutral among the preparation method that the present invention adopted, and no acid and alkali corrosion property can increase duration of service, and need not wash; The content of synthetic anode material for lithium-ion batteries cobalt further reduces, and has more reduced the pollution to environment when having reduced production cost, and the positive electrode specific capacity height, the good cycle that behind overcompaction, are synthesized, that technology simply reaches cost is low.
Description of drawings
Fig. 1 is positive electrode Li [Li
0.2Mn
0.54Ni
0.13Co
0.08Al
0.05] O
2XRD figure.
Fig. 2 is positive electrode Li [Li
0.2Mn
0.54Ni
0.13Co
0.08Al
0.05] O
2SEM figure.
Fig. 3 is positive electrode Li [Li
0.2Mn
0.54Ni
0.13Co
0.08Cr
0.05] O
2First charge-discharge curve (2.0～4.8V, 0.1C, room temperature).
The abscissa of Fig. 1 is sweep limits 2 θ (10～90 °), and ordinate is the intensity at peak.The times magnification of Fig. 2 is 50000 times.The abscissa of Fig. 3 is a specific capacity, and mAh/g, ordinate are voltage, and unit is V, and curve A is meant charging curve among Fig. 3, and curve B is meant discharge curve.
Embodiment
Below in conjunction with concrete accompanying drawing and embodiment the present invention is described further.
Embodiment one: a kind of preparation method of anode material for lithium-ion batteries, adopt following processing step:
(1) be 1.236: 0.54: 0.13 in molar ratio with lithium nitrate, manganese acetate, nickel nitrate, cobalt nitrate and aluminum nitrate: 0.08: 0.05 (wherein in order to prevent a small amount of volatilization of lithium under the hot environment; Lithium nitrate excessive 3%) mixes; Under stirring condition, be dissolved in the deionized water; The total concentration of lithium nitrate, manganese acetate, nickel nitrate, cobalt nitrate and aluminum nitrate is 0.2mol/L, and mixing speed is 90 rev/mins, and mixing time is 30 minutes; Add the aqueous citric acid solution that concentration is 0.5mol/L again, low whipping speed is that to drip mass percentage concentration under 90 rev/mins the condition be that to regulate the pH value be 6 for 15% ammonia spirit again; The total amount of said manganese acetate, nickel nitrate, cobalt nitrate and aluminum nitrate and the mol ratio of citric acid are 1: 0.9;
(2) under 50 ℃ condition, carried out evaporation at constant temperature 10 hours under the condition that the mixed solution low whipping speed that step (1) is obtained is 200 rev/mins, obtain colloidal sol;
(3) colloidal sol is placed air dry oven under 80 ℃ of conditions dry 12 hours, drive away moisture, obtain xerogel with evaporation;
(4) place Muffle furnace to calcine xerogel, programming rate is 1 ℃/min, is warming up to 200 ℃, calcines 20 hours, obtains presoma;
(5) presoma is cooled to after the room temperature grinding in ball grinder 0.5 hour; Presoma compacting after grinding is placed in the Muffle furnace; In excess oxygen or air atmosphere under calcine, programming rate is 3 ℃/min, is warming up to 700 ℃; Calcined 30 hours, and promptly obtained described anode material for lithium-ion batteries Li [Li after being cooled to room temperature
0.2Mn
0.54Ni
0.13Co
0.08Al
0.05] O
2
The positive electrode that embodiment one is obtained is assembled into CR2032 type button cell and carries out the charge and discharge cycles test.Adopt coating method to prepare electrode; With N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent; Respectively take by weighing positive electrode, acetylene black at 80: 12: 8 and gather inclined to one side tetrafluoroethene (PVDF) by mass ratio; After ground and mixed is even, be coated on the pretreated aluminium foil, put into vacuum drying chamber and obtain positive plate 80 ℃ of dryings.The pure metal lithium sheet is made negative pole, and microporous polypropylene membrane Celgard 2325 is a barrier film, and the mixed solution of LB315 [m (DMC): m (EMC): m (EC)=1: 1: 1] is as electrolyte, (H in being full of the argon gas glove box
2O content＜1ppm) is assembled into simulated battery.Carry out constant current cycle charge discharge electrical testing with LAND battery test system button type battery; At test voltage 2.0～4.8V, 0.1C discharges and recharges under the condition, and the room temperature specific discharge capacity is 262.7mAh/g, and capability retention can be higher than 92% after 60 charge and discharge cycles.
Embodiment two: a kind of preparation method of anode material for lithium-ion batteries, adopt following processing step:
(1) be 1.248: 0.54: 0.13 in molar ratio with lithium hydroxide, manganese acetate, nickel nitrate, cobalt nitrate and chromic nitrate: 0.08: 0.05 (wherein in order to prevent a small amount of volatilization of lithium under the hot environment; Lithium hydroxide excessive 4%) mixes; Under stirring condition, be dissolved in the deionized water; The total concentration of lithium hydroxide, manganese acetate, nickel nitrate, cobalt nitrate and chromic nitrate is 1mol/L, and mixing speed is 100 rev/mins, and mixing time is 25 minutes; Add the aqueous citric acid solution that concentration is 1mol/L again, low whipping speed is that to drip mass percentage concentration under 100 rev/mins the condition be that to regulate the pH value be 7 for 16% ammonia spirit again; The total amount of said manganese acetate, nickel nitrate, cobalt nitrate and chromic nitrate and the mol ratio of citric acid are 1: 1;
(2) under 60 ℃ condition, carried out evaporation at constant temperature 8 hours under the condition that the mixed solution low whipping speed that step (1) is obtained is 300 rev/mins, obtain colloidal sol;
(3) colloidal sol is placed air dry oven under 90 ℃ of conditions dry 10 hours, drive away moisture, obtain xerogel with evaporation;
(4) place Muffle furnace to calcine xerogel, programming rate is 2 ℃/min, is warming up to 300 ℃, calcines 18 hours, obtains presoma;
(5) presoma is cooled to after the room temperature grinding in ball grinder 0.6 hour; Presoma compacting after grinding is placed in the Muffle furnace; In excess oxygen or air atmosphere under calcine, programming rate is 4 ℃/min, is warming up to 800 ℃; Calcined 25 hours, and promptly obtained described anode material for lithium-ion batteries Li [Li after being cooled to room temperature
0.2Mn
0.54Ni
0.13Co
0.08Cr
0.05] O
2
The positive electrode that embodiment two is obtained is assembled into CR2032 type button cell and carries out the charge and discharge cycles test.Carry out constant current cycle charge discharge electrical testing with LAND battery test system button type battery; At test voltage 2.0～4.8V, 0.1C discharges and recharges under the condition, and the room temperature specific discharge capacity is 274.9mAh/g, and capability retention can reach 91.5% after 60 charge and discharge cycles.
Embodiment three: a kind of preparation method of anode material for lithium-ion batteries, adopt following processing step:
(1) be 1.242: 0.55: 0.1 in molar ratio with lithium acetate, manganese nitrate, nickel nitrate, cobalt nitrate and ferric nitrate: 0.1: 0.05 (wherein in order to prevent a small amount of volatilization of lithium under the hot environment; Lithium salts excessive 3.5%) mixes; Under stirring condition, be dissolved in the deionized water; The total concentration of lithium acetate, manganese nitrate, nickel nitrate, cobalt nitrate and ferric nitrate is 2mol/L, and mixing speed is 110 rev/mins, and mixing time is 20 minutes; Add the aqueous citric acid solution that concentration is 1.5mol/L again, low whipping speed is that to drip mass percentage concentration under 110 rev/mins the condition be that to regulate the pH value be 6.5 for 17% ammonia spirit again; The total amount of said manganese nitrate, nickel nitrate, cobalt nitrate and ferric nitrate and the mol ratio of citric acid are 1: 1.1;
(2) under 70 ℃ condition, carried out evaporation at constant temperature 6 hours under the condition that the mixed solution low whipping speed that step (1) is obtained is 400 rev/mins, obtain colloidal sol;
(3) colloidal sol is placed air dry oven under 100 ℃ of conditions dry 8 hours, drive away moisture, obtain xerogel with evaporation;
(4) place Muffle furnace to calcine xerogel, programming rate is 3 ℃/min, is warming up to 400 ℃, calcines 16 hours, obtains presoma;
(5) presoma is cooled to after the room temperature grinding in ball grinder 0.8 hour; Presoma compacting after grinding is placed in the Muffle furnace; In excess oxygen or air atmosphere under calcine, programming rate is 5 ℃/min, is warming up to 900 ℃; Calcined 20 hours, and promptly obtained described anode material for lithium-ion batteries Li [Li after being cooled to room temperature
0.2Mn
0.55Ni
0.1Co
0.1Fe
0.05] O
2
The positive electrode that embodiment three is obtained is assembled into CR2032 type button cell and carries out the charge and discharge cycles test.Carry out constant current cycle charge discharge electrical testing with LAND battery test system button type battery; At test voltage 2.0～4.8V, 0.1C discharges and recharges under the condition, and the room temperature specific discharge capacity is 231.9mAh/g, and capability retention can reach 96% after 60 charge and discharge cycles.
Embodiment four: a kind of preparation method of anode material for lithium-ion batteries, adopt following processing step:
(1) be 1.2432: 0.54: 0.13 in molar ratio with lithium nitrate, manganese acetate, nickel nitrate, cobalt acetate and aluminum nitrate: 0.03: 0.1 (wherein in order to prevent a small amount of volatilization of lithium under the hot environment; Lithium salts excessive 3.6%) mixes; Under stirring condition, be dissolved in the deionized water; The total concentration of lithium nitrate, manganese acetate, nickel nitrate, cobalt acetate and aluminum nitrate is 3mol/L, and mixing speed is 120 rev/mins, and mixing time is 15 minutes; Add the aqueous citric acid solution that concentration is 2mol/L again, low whipping speed is that to drip mass percentage concentration under 120 rev/mins the condition be that to regulate the pH value be 7.5 for 18% ammonia spirit again; The total amount of said manganese acetate, nickel nitrate, cobalt acetate and aluminum nitrate and the mol ratio of citric acid are 1: 1;
(2) under 80 ℃ condition, carried out evaporation at constant temperature 5 hours under the condition that the mixed solution low whipping speed that step (1) is obtained is 450 rev/mins, obtain colloidal sol;
(3) colloidal sol is placed air dry oven under 120 ℃ of conditions dry 6 hours, drive away moisture, obtain xerogel with evaporation;
(4) place Muffle furnace to calcine xerogel, programming rate is 4 ℃/min, is warming up to 500 ℃, calcines 15 hours, obtains presoma;
(5) presoma is cooled to after the room temperature grinding in ball grinder 1 hour; Presoma compacting after grinding is placed in the Muffle furnace; In excess oxygen or air atmosphere under calcine, programming rate is 6 ℃/min, is warming up to 1000 ℃; Calcined 15 hours, and promptly obtained described anode material for lithium-ion batteries Li [Li after being cooled to room temperature
0.2Mn
0.54Ni
0.13Co
0.03Al
0.1] O
2
The positive electrode that embodiment four is obtained is assembled into CR2032 type button cell and carries out the charge and discharge cycles test.Carry out constant current cycle charge discharge electrical testing with LAND battery test system button type battery; At test voltage 2.0～4.8V, 0.1C discharges and recharges under the condition, and the room temperature specific discharge capacity is 248.6mAh/g, and capability retention can reach 92.3% after 60 charge and discharge cycles.
Embodiment five: a kind of preparation method of anode material for lithium-ion batteries, adopt following processing step:
(1) be 1.2444: 0.54: 0.13 in molar ratio with lithium carbonate, manganese acetate, nickelous sulfate, cobaltous sulfate and magnesium sulfate: 0.08: 0.05 (wherein in order to prevent a small amount of volatilization of lithium under the hot environment; Lithium salts excessive 3.7%) mixes; Under stirring condition, be dissolved in the deionized water; The total concentration of lithium carbonate, manganese acetate, nickelous sulfate, cobaltous sulfate and magnesium sulfate is 6mol/L, and mixing speed is 180 rev/mins, and mixing time is 10 minutes; Add the aqueous citric acid solution that concentration is 3mol/L again, low whipping speed is that to drip mass percentage concentration under 180 rev/mins the condition be that to regulate the pH value be 8 for 28% ammonia spirit again; The total amount of said manganese acetate, nickelous sulfate, cobaltous sulfate and magnesium sulfate and the mol ratio of citric acid are 1: 1.2;
(2) under 90 ℃ condition, carried out evaporation at constant temperature 4 hours under the condition that the mixed solution low whipping speed that step (1) is obtained is 500 rev/mins, obtain colloidal sol;
(3) colloidal sol is placed air dry oven under 180 ℃ of conditions dry 4 hours, drive away moisture, obtain xerogel with evaporation;
(4) place Muffle furnace to calcine xerogel, programming rate is 5 ℃/min, is warming up to 600 ℃, calcines 2 hours, obtains presoma;
(5) presoma is cooled to after the room temperature grinding in ball grinder 2 hours; Presoma compacting after grinding is placed in the Muffle furnace; In excess oxygen or air atmosphere under calcine, programming rate is 8 ℃/min, is warming up to 1100 ℃; Calcined 3 hours, and promptly obtained described anode material for lithium-ion batteries Li [Li after being cooled to room temperature
0.2Mn
0.54Ni
0.13Co
0.08Mg
0.05] O
2
The positive electrode that embodiment five is obtained is assembled into CR2032 type button cell and carries out the charge and discharge cycles test.Carry out constant current cycle charge discharge electrical testing with LAND battery test system button type battery; At test voltage 2.0～4.8V, 0.1C discharges and recharges under the condition, and the room temperature specific discharge capacity is 254.4mAh/g, and capability retention can reach 91.6% after 60 charge and discharge cycles.
Claims (5)
1. anode material for lithium-ion batteries, it is characterized in that: the chemical general formula of said positive electrode is Li [Li
aMn
bNi
cCo
dM
e] O
2, wherein 0.05≤a≤0.25,0.4≤b≤0.8,0.03≤c, d, e≤0.15, and a+b+c+d+e=1, M is one or more among Al, Cr, Ti, the Mg.
2. the preparation method of an anode material for lithium-ion batteries is characterized in that, adopts following processing step:
(1) lithium salts, manganese salt, nickel salt, cobalt salt and M salt are dissolved in the deionized water under stirring condition, the total concentration of lithium salts, manganese salt, nickel salt, cobalt salt and M salt is 0.2～6mol/L, and mixing speed is 90～180 rev/mins, and mixing time is 10～60 minutes; Add the complexing agent aqueous solution that concentration is 0.5～3mol/L again, low whipping speed is that to drip mass percentage concentration under 90～180 rev/mins the condition be that to regulate the pH value be 6～8 for 15～28% ammonia spirit again; The mol ratio of said lithium salts, manganese salt, nickel salt, cobalt salt and M salt is 1～1.25: 0.4～0.8: 0.03～0.15: 0.03～0.15: 0.03～0.15, and M salt is one or more in aluminium salt, chromic salts, titanium salt, the magnesium salts; The total amount of said manganese salt, nickel salt, cobalt salt and M salt and the mol ratio of complexing agent are 1: 0.9～1.2;
(2) under 50～90 ℃ condition, carried out evaporation at constant temperature 4～10 hours under the condition that the mixed solution low whipping speed that step (1) is obtained is 200～500 rev/mins, obtain colloidal sol;
(3) colloidal sol is placed air dry oven under 80～180 ℃ of conditions dry 4～12 hours, drive away moisture, obtain xerogel with evaporation;
(4) place Muffle furnace to calcine xerogel, programming rate is 1～5 ℃/min, is warming up to 200～600 ℃, calcines 2～20 hours, obtains presoma;
(5) presoma is cooled to after the room temperature grinding in ball grinder 0.5～2 hour; Presoma compacting after grinding is placed in the Muffle furnace; In excess oxygen or air atmosphere under calcine, programming rate is 3～8 ℃/min, is warming up to 700～1100 ℃; Calcined 3～30 hours, and promptly obtained described anode material for lithium-ion batteries Li [Li after being cooled to room temperature
aMn
bNi
cCo
dM
e] O
2
3. like the preparation method of the said anode material for lithium-ion batteries of claim 2, it is characterized in that: said lithium salts is one or more in lithium carbonate, lithium nitrate, lithium acetate, the lithium hydroxide; Said manganese salt is one or more in manganese sulfate, manganese nitrate, the manganese acetate; Said nickel salt is one or more in nickelous sulfate, nickel nitrate, the nickel acetate; Said cobalt salt is one or more in cobaltous sulfate, cobalt nitrate, the cobalt acetate; Said aluminium salt is one or more in aluminum sulfate, aluminum nitrate and the lithium acetate; Said chromic salts is one or more in chromium sulfate, chromic nitrate and the chromium acetate; Said titanium salt is one or more in titanium sulfate, Titanium Nitrate, the acetate titanium; Said magnesium salts is one or more in magnesium nitrate, magnesium sulfate, the magnesium acetate.
4. like the preparation method of the said anode material for lithium-ion batteries of claim 2, it is characterized in that: said complexing agent aqueous solution is one or more the aqueous solution in citric acid, tartaric acid, the ethylene glycol.
5. like the preparation method of the said anode material for lithium-ion batteries of claim 2, it is characterized in that: in the step (5), said excess oxygen is that oxygen concentration is greater than 21%.
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