CN102340004A - Lithium ion phosphate cathode material of lithium ion battery and preparation method - Google Patents
Lithium ion phosphate cathode material of lithium ion battery and preparation method Download PDFInfo
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- CN102340004A CN102340004A CN2011102963081A CN201110296308A CN102340004A CN 102340004 A CN102340004 A CN 102340004A CN 2011102963081 A CN2011102963081 A CN 2011102963081A CN 201110296308 A CN201110296308 A CN 201110296308A CN 102340004 A CN102340004 A CN 102340004A
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Abstract
The invention provides a lithium ion phosphate cathode material and a lithium ion battery and a preparation method. F<-> anions are doped with lithium ion phosphate to obtain a composite material Li(1+x)FePO4Fx. A fluorine source is mixed with a lithium source, an ion source and a phosphorus source based on a solid phase sintering method; a given organic solution is taken as a solvent and uniformly ball-milled and mixed with the mixture, and a precursor is obtained by using spray drying under the protection of an inert gas; and the precursor is sintered for 4 to 10h at the constant temperature of 300 to 450 DEG C in an inert protection atmosphere, sintered for 8 to 20h at the constant temperature of 500 to 800 DEG C and cooled to room temperature to obtain the composite material Li(1+x)FePO4Fx obtained by doping the F<-> anions and the lithium ion phosphate. The preparation method is based on the solid phase sintering method and easy to commercially use; a doping process is simple and practical; and the prepared composite material Li(1+x)FePO4Fx has high electrochemical performance, high lithium ion deintercalation/intercalation reversibility and vast application prospect.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof, specifically, the present invention relates to a kind of lithium iron (II) phosphate anode of lithium ion battery material and preparation method thereof, belong to the anode material for lithium-ion batteries technology.
Background technology
Fossil fuels such as oil, coal, natural gas are the bases of the economy of energy.Exhausted and the use of fossil fuel resource becomes two difficult problems that current social development faces to the Ecological environment worsening problem.Get into 21 century; Characteristics such as the utilization of renewable resources such as environment amenable wind energy, solar energy, tidal energy becomes the human key that solves energy problem, and lithium ion battery relies on its energy density height, non-environmental-pollution, have extended cycle life become the desirable storage medium of clean energy resource.In recent years, along with the demand increase of electric automobile and energy-storage system, the lithium ion battery energy storage device that has high power and high-energy-density becomes the emphasis of current research, has obtained tremendous development.
1997, the John. B. Goodenough of texas,U.S university etc. reported LiFePO
4Invertibity embed the characteristic of lithium ion, make this LiMPO that has olivine structural
4Material has obtained global very big attention, and has obtained extensive studies and development rapidly.With respect to the anode material for lithium-ion batteries of other types, LiFePO
4Material price is cheap, and fail safe is good, have extended cycle life, and theoretical capacity big (can reach 170mAh/g), and have fewer environmental impacts.LiFePO
4These performances of material satisfy the requirement of electric automobile development fully, are the desirable anode materials of used for electric vehicle lithium battery.
Yet, LiFePO
4Bad electronic conductivity (10
-9-10
-10S/cm) and lower lithium ion mobility (D
Li +<10
-14Cm
2/ s) becoming the difficult problem of this material large-scale application, a large amount of both at home and abroad research institution and enterprises have carried out deep research to these two problems.The raising LiFePO that extensively adopts both at home and abroad at present
4The method of material property mainly comprises carbon coating technology, metal cation doping techniques, anion doped technology and nanometer micronizing technology.
Domestic employing anion F
-The conventional method of the patented technology of mixing is to use fluoride ion source to use as catalyst; The effect of fluorine ion is to promote LiFePO4 synthetic reaction process; Do not get into the LiFePO4 end product, for example patent 200810142216 is added fluorine ion and is reduced reaction activity in LiFePO 4; Or use anion F
-Substitute the O in the LiFePO 4
2-Or PO
4 2-Improve the ferrousphosphate lithium material chemical property, for example patent 200510112562 uses anion oxygen place doped at LiFePO4, and patent 20100204521 is used anion F
-Substitute the phosphate radical in the LiFePO 4.
Summary of the invention
The invention provides anion doped nanometer ferrous phosphate lithium positive electrode of a kind of lithium battery and preparation method thereof, through anion F
-Doping, can effectively promote the electronic conductivity of LiFePO 4, significantly improve the chemical property of LiFePO 4.
In order to realize the foregoing invention purpose, its concrete technical scheme is following:
A kind of lithium iron (II) phosphate anode of lithium ion battery material is characterized in that: adopt F
-Anion doped LiFePO 4, the acquisition chemical formula is Li
(1+x)FePO
4F
xThe lithium iron (II) phosphate anode of lithium ion battery material, wherein x is 0.001～0.05; Under the 1C multiplying power first discharge capacity be 135～155mAh/g, circulating after 50 times, discharge capacity is 133～152mAh/g under the 1C multiplying power.
A kind of lithium iron (II) phosphate anode of lithium ion battery preparation methods is characterized in that, comprises following processing step:
A, get lithium-containing compound, contain ferro-compound, phosphorus-containing compound and fluorochemical be Li:Fe:P:F=(1.001～1.05): 1:1 in mol ratio between atom: the ratio of (0.001～0.05) is carried out batch mixing; Every 1mol reactant add 500ml～2500ml ball milling with the chemical pure organic solvent as solvent; Place polytetrafluoroethylene ball grinder ball milling 8～16 hours, and obtained the presoma suspension-turbid liquid;
B, this presoma suspension-turbid liquid is transported in the spray dryer through measuring pump, under inert gas shielding, carries out drying-granulating, precursor suspension-turbid liquid feed flow is 0.05～0.3L/min, and EAT is 200～250 ℃, and leaving air temp is 90～120 ℃;
C, the powder that will pass through behind the drying-granulating place tube furnace; Under the protection of slumpability gas or mobile reducing gas; At first the speed with 5 ℃/min is warming up to 300～450 ℃, constant temperature roast 4～10 hours, and the speed with 5 ℃/min is warming up to 500～800 ℃ then; Constant temperature roast 8～20 hours has obtained anion F
～The ferrous phosphate powder for lithium that mixes is a lithium iron (II) phosphate anode of lithium ion battery material of the present invention.
The lithium-containing compound described in the steps A of the present invention be in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate and the lithium nitrate one or several arbitrarily than mixture.
Contain described in the steps A of the present invention ferro-compound be in ferrous oxalate, ferrous acetate, ferrous oxide and the ferrous nitrate one or several arbitrarily than mixture.
Phosphorus-containing compound described in the steps A of the present invention be in diammonium hydrogen phosphate, ammonium dihydrogen phosphate and the ammonium phosphate one or several arbitrarily than mixture.
Fluorochemical described in the steps A of the present invention be in lithium fluoride, ammonium fluoride, sodium fluoride and the potassium fluoride one or several arbitrarily than mixture.
Ball milling described in the steps A of the present invention use the chemical pure organic solvent as in methyl alcohol, ethanol, acetone, isopropyl alcohol and the ethyl acetate one or several arbitrarily than mixture.
Slumpability gas of the present invention is nitrogen or argon gas, and described mobile reducing gas is a hydrogen.
Preparation method according to the invention also has following beneficial effect:
1, adopting solid sintering technology is the basis, is easy to commercial applications, and doping process is simple and practical, prepared Li<sub >(1+x)</sub>FePO<sub >4</sub>F<sub >x</sub>(0.001<x<0.05) material electrochemical performance is outstanding, under the 1C multiplying power first discharge capacity be not less than 135mAhg.
2, adopt F
-Anion is different from other ion doping schemes as dopant ion, has unique crystal structure, and this composite material is not replaced the crystal intermediate ion, so crystal structure is stable, has good lithium ion and takes off/the embedding invertibity.
3, in the employing spray dryer precursor is carried out drying, contrast traditional drying technology, the precursor drying effect is faster and can realize the granulation to precursor, can improve follow-up solid-phase sintering effect, and the sintered product particle size distribution is even.
4, adopt ion doping technique can effectively improve the lithium ion transition condition, because the ferrousphosphate lithium material lattice structure is stable, the present invention uses anion F
-Mix, the ferrous phosphate crystalline lithium is not carried out the ion replacement, but form Li
(1+x)FePO
4F
xComposite construction can effectively improve the lithium iron phosphate electrochemical performance when reducing the reaction difficulty.
Description of drawings
Fig. 1 is the prepared Li of instance 1～4
(1+x)FePO
4F
xThe discharge curve of the button cell that composite material is equipped under 1C (1C=170mA/g) multiplying power, the wherein discharge curve of A, B, C, 1～4 packed battery of D difference corresponding instance.
Fig. 2 is the prepared Li of instance 1～4
(1+x)FePO
4F
xThe performance curve that circulation discharges and recharges for 50 times under button cell 1C (1C=170mA/g) multiplying power that composite material is equipped, the wherein cyclic curve of a, b, c, 1～4 packed battery of d difference corresponding instance.
Embodiment
Embodiment 1
Get 0.05mol Li
2CO
3, 0.1mol FeC
2O
4, 0.1mol NH
4H
2PO
3And 0.002mol LiF is that raw materials mix is inserted in the polytetrafluoroethylene ball grinder, adds the 100ml absolute ethyl alcohol, and ball milling obtained the precursor slurry in 12 hours.With the precursor slurry through measuring pump with the flow volume delivery of 0.1 L/min to spray dryer, under inert gas shielding, EAT is 220 ℃, leaving air temp is 110 ℃, from powder collector, obtains dry precursor powder.This precursor powder is inserted in the tube furnace, and the speed with 5 ℃/min under the argon shield of flowing is warming up to 350 ℃ of maintenances 8 hours, and the speed with 5 ℃/min is warming up to 600 ℃ of maintenances 16 hours again, after the automatic slow cooling of tube furnace to room temperature, obtains end product Li
1.02FePO
4F
0.02Powder.
With organic solvent 1-methyl-2 pyrrolidones (NMP) is solvent; After the electrode material for preparing, conductive agent (acetylene black) and binding agent Kynoar (PVDF) pressed mass ratio 75:15:10 mixing and stirring; Being evenly coated in diameter is on the aluminum foil current collector of 14 mm; 75 ℃ of oven dry in drying box are used the tablet press machine compacting evenly then, make electrode slice to be measured.Adopt the button type simulated battery that prepared electrode slice is carried out the battery assembling.Be metal lithium sheet to electrode wherein, barrier film is Celgard 2325 composite membranes, and electrolyte is 1 mol/L LiPF
6Equal-volume than ethylene carbonate (EC), dimethyl carbonic ether (DMC) solution, battery pack is contained in the glove box that is full of argon gas and accomplishes.Battery is done the constant current charge-discharge test between 2.5 ~ 4.2 V voltage ranges.The discharge curve of battery under 1C (1C=170mA/g) multiplying power that the positive electrode of instance 1 preparation is adorned shown in A curve among Fig. 1, its first discharge capacity be 140mAh/g.The performance curve that the battery that the positive electrode of instance 1 preparation is adorned discharges and recharges for 100 times in circulation under the 1C multiplying power is shown in a curve among Fig. 2, and discharge capacity is 138mAh/g after its circulation 50 times.
Get 0.1025mol LiOH, 0.1mol Fe (CH
3COO)
2, 0.1mol (NH
4)
3PO
3And 0.0025mol NH
4F is that raw materials mix is inserted in the polytetrafluoroethylene ball grinder, adds 100ml acetone, and ball milling obtained the precursor slurry in 10 hours.With the precursor slurry through measuring pump with the flow volume delivery of 0.1 L/min to spray dryer, under inert gas shielding, EAT is 220 ℃, leaving air temp is 110 ℃, from powder collector, obtains dry precursor powder.This precursor powder is inserted in the tube furnace, and the speed with 5 ℃/min under the argon shield of flowing is warming up to 320 ℃ of maintenances 10 hours, and the speed with 5 ℃/min is warming up to 650 ℃ of maintenances 12 hours again, after the automatic slow cooling of tube furnace to room temperature, obtains end product Li
1.025FePO
4F
0.025Powder.
Adopt instance 1 said button cell manufacture method, instance 2 prepared positive electrodes are made into button cell between 2.5 ~ 4.2 V voltage ranges, do the constant current charge-discharge test.The battery that the positive electrode of instance 2 preparation is adorned at the discharge curve under the 1C multiplying power shown in B curve among Fig. 1, its first discharge capacity be 137mAh/g.The performance curve that the battery that the positive electrode of instance 2 preparation is adorned discharges and recharges for 50 times in circulation under the 1C multiplying power is shown in b curve among Fig. 2, and discharge capacity is 135mAh/g after its circulation 100 times.
Embodiment 3
Get 0.1515mol Li
2CO
3, 0.3mol Fe (CH
3COO)
2, 0.3mol (NH
4)
2HPO
3And 0.003mol NaF is that raw materials mix is inserted in the polytetrafluoroethylene ball grinder, adds the 250ml isopropyl alcohol, and ball milling obtained the precursor slurry in 12 hours.With the precursor slurry through measuring pump with the flow volume delivery of 0.1 L/min to spray dryer, under inert gas shielding, EAT is 220 ℃, leaving air temp is 110 ℃, from powder collector, obtains dry precursor powder.This precursor powder is inserted in the tube furnace, and the speed with 5 ℃/min under the argon shield of flowing is warming up to 400 ℃ of maintenances 6 hours, and the speed with 5 ℃/min is warming up to 700 ℃ of maintenances 12 hours again, after the automatic slow cooling of tube furnace to room temperature, obtains end product Li
1.01FePO
4F
0.01Powder.
Adopt instance 1 said button cell manufacture method, instance 3 prepared positive electrodes are made into button cell between 2.5 ~ 4.2 V voltage ranges, do the constant current charge-discharge test.The discharge curve of battery under the 1C multiplying power that the positive electrode of instance 3 preparation is adorned shown in C curve among Fig. 1, its first discharge capacity be 135mAh/g.The performance curve that the battery that the positive electrode of instance 3 preparation is adorned discharges and recharges for 50 times in circulation under the 1C multiplying power is shown in c curve among Fig. 2, and discharge capacity is 133mAh/g after its circulation 100 times.
Get 0.200mol CH
3COOLi, 0.2mol FeC
2O
4, 0.2mol (NH
4)
2HPO
3And 0.008mol LiF is that raw materials mix is inserted in the polytetrafluoroethylene ball grinder, adds the 150ml absolute ethyl alcohol, and ball milling obtained the precursor slurry in 14 hours.With the precursor slurry through measuring pump with the flow volume delivery of 0.1 L/min to spray dryer, under inert gas shielding, EAT is 220 ℃, leaving air temp is 110 ℃, from powder collector, obtains dry precursor powder.This precursor powder is inserted in the tube furnace, and the speed with 5 ℃/min under the argon shield of flowing is warming up to 420 ℃ of maintenances 6 hours, and the speed with 5 ℃/min is warming up to 720 ℃ of maintenances 15 hours again, after the automatic slow cooling of tube furnace to room temperature, obtains end product Li
1.04FePO
4F
0.04Powder.
Adopt instance 1 said button cell manufacture method, instance 4 prepared positive electrodes are made into button cell between 2.5 ~ 4.2 V voltage ranges, do the constant current charge-discharge test.The battery that the positive electrode of instance 4 preparation is adorned at the discharge curve under the 1C multiplying power shown in D curve among Fig. 1, its first discharge capacity be 139mAh/g.The performance curve that the battery that the positive electrode of instance 4 preparation is adorned discharges and recharges for 50 times in circulation under the 1C multiplying power is shown in d curve among Fig. 2, and discharge capacity is 137mAh/g after its circulation 100 times.
Embodiment 5
A kind of lithium iron (II) phosphate anode of lithium ion battery material is characterized in that: adopt F
-Anion doped LiFePO 4, the acquisition chemical formula is Li
(1+x)FePO
4F
xThe lithium iron (II) phosphate anode of lithium ion battery material, wherein x is 0.001; Under the 1C multiplying power first discharge capacity be 135mAh/g, circulating after 50 times, discharge capacity is 133mAh/g under the 1C multiplying power.
A kind of lithium iron (II) phosphate anode of lithium ion battery material is characterized in that: adopt F
-Anion doped LiFePO 4, the acquisition chemical formula is Li
(1+x)FePO
4F
xThe lithium iron (II) phosphate anode of lithium ion battery material, wherein x is 0.05; Under the 1C multiplying power first discharge capacity be 145mAh/g, circulating after 50 times, discharge capacity is 142.5mAh/g under the 1C multiplying power.
Embodiment 7
A kind of lithium iron (II) phosphate anode of lithium ion battery material is characterized in that: adopt F
-Anion doped LiFePO 4, the acquisition chemical formula is Li
(1+x)FePO
4F
xThe lithium iron (II) phosphate anode of lithium ion battery material, wherein x is 0.025; Under the 1C multiplying power first discharge capacity be 155mAh/g, circulating after 50 times, discharge capacity is 152mAh/g under the 1C multiplying power.
A kind of lithium iron (II) phosphate anode of lithium ion battery material is characterized in that: adopt F
-Anion doped LiFePO 4, the acquisition chemical formula is Li
(1+x)FePO
4F
xThe lithium iron (II) phosphate anode of lithium ion battery material, wherein x is 0.04; Under the 1C multiplying power first discharge capacity be 148mAh/g, circulating after 50 times, discharge capacity is 145mAh/g under the 1C multiplying power.
Embodiment 9
A, get lithium-containing compound, contain ferro-compound, phosphorus-containing compound and fluorochemical be that the ratio of Li:Fe:P:F=1.001:1:1:0.001 is carried out batch mixing in mol ratio between atom; Every 1mol reactant add the 500ml ball milling with the chemical pure organic solvent as solvent; Place polytetrafluoroethylene ball grinder ball milling 8 hours, and obtained the presoma suspension-turbid liquid;
B, this presoma suspension-turbid liquid is transported in the spray dryer through measuring pump, under inert gas shielding, carries out drying-granulating, precursor suspension-turbid liquid feed flow is 0.05L/min, and EAT is 200 ℃, and leaving air temp is 90 ℃.
C, the powder that will pass through behind the drying-granulating place tube furnace; Under the protection of slumpability gas or mobile reducing gas; At first the speed with 5 ℃/min is warming up to 300 ℃, constant temperature roast 4 hours, and the speed with 5 ℃/min is warming up to 500 ℃ then; Constant temperature roast 8 hours has obtained anion F
-The ferrous phosphate powder for lithium that mixes is a lithium iron (II) phosphate anode of lithium ion battery material of the present invention.
Preferred version further is:
Lithium-containing compound described in the steps A be in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate and the lithium nitrate one or several arbitrarily than mixture.
Contain ferro-compound described in the steps A and be in ferrous oxalate, ferrous acetate, ferrous oxide and the ferrous nitrate one or several arbitrarily than mixture.
Phosphorus-containing compound described in the steps A be in diammonium hydrogen phosphate, ammonium dihydrogen phosphate and the ammonium phosphate one or several arbitrarily than mixture.
Fluorochemical described in the steps A be in lithium fluoride, ammonium fluoride, sodium fluoride and the potassium fluoride one or several arbitrarily than mixture.
Ball milling described in the steps A use the chemical pure organic solvent as in methyl alcohol, ethanol, acetone, isopropyl alcohol and the ethyl acetate one or several arbitrarily than mixture.
Described slumpability gas is nitrogen or argon gas.
Described mobile reducing gas is a hydrogen.
A, get lithium-containing compound, contain ferro-compound, phosphorus-containing compound and fluorochemical be that the ratio of Li:Fe:P:F=1.05:1:1:0.05 is carried out batch mixing in mol ratio between atom; Every 1mol reactant add the 2500ml ball milling with the chemical pure organic solvent as solvent; Place polytetrafluoroethylene ball grinder ball milling 16 hours, and obtained the presoma suspension-turbid liquid;
B, this presoma suspension-turbid liquid is transported in the spray dryer through measuring pump, under inert gas shielding, carries out drying-granulating, precursor suspension-turbid liquid feed flow is 0.3L/min, and EAT is 250 ℃, and leaving air temp is 120 ℃.
C, the powder that will pass through behind the drying-granulating place tube furnace; Under the protection of slumpability gas or mobile reducing gas; At first the speed with 5 ℃/min is warming up to 450 ℃, constant temperature roast 10 hours, and the speed with 5 ℃/min is warming up to 800 ℃ then; Constant temperature roast 20 hours has obtained anion F
-The ferrous phosphate powder for lithium that mixes is a lithium iron (II) phosphate anode of lithium ion battery material of the present invention.
Preferred version further is:
Lithium-containing compound described in the steps A be in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate and the lithium nitrate one or several arbitrarily than mixture.
Contain ferro-compound described in the steps A and be in ferrous oxalate, ferrous acetate, ferrous oxide and the ferrous nitrate one or several arbitrarily than mixture.
Phosphorus-containing compound described in the steps A be in diammonium hydrogen phosphate, ammonium dihydrogen phosphate and the ammonium phosphate one or several arbitrarily than mixture.
Fluorochemical described in the steps A be in lithium fluoride, ammonium fluoride, sodium fluoride and the potassium fluoride one or several arbitrarily than mixture.
Ball milling described in the steps A use the chemical pure organic solvent as in methyl alcohol, ethanol, acetone, isopropyl alcohol and the ethyl acetate one or several arbitrarily than mixture.
Described slumpability gas is nitrogen or argon gas.
Described mobile reducing gas is a hydrogen.
Embodiment 11
A, get lithium-containing compound, contain ferro-compound, phosphorus-containing compound and fluorochemical be that the ratio of Li:Fe:P:F=1.025:1:1:0.025 is carried out batch mixing in mol ratio between atom; Every 1mol reactant add the 1500ml ball milling with the chemical pure organic solvent as solvent; Place polytetrafluoroethylene ball grinder ball milling 12 hours, and obtained the presoma suspension-turbid liquid;
B, this presoma suspension-turbid liquid is transported in the spray dryer through measuring pump, under inert gas shielding, carries out drying-granulating, precursor suspension-turbid liquid feed flow is 0.175L/min, and EAT is 225 ℃, and leaving air temp is 105 ℃.
C, the powder that will pass through behind the drying-granulating place tube furnace; Under the protection of slumpability gas or mobile reducing gas; At first the speed with 5 ℃/min is warming up to 375 ℃, constant temperature roast 7 hours, and the speed with 5 ℃/min is warming up to 650 ℃ then; Constant temperature roast 14 hours has obtained anion F
-The ferrous phosphate powder for lithium that mixes is a lithium iron (II) phosphate anode of lithium ion battery material of the present invention.
Preferred version further is:
Lithium-containing compound described in the steps A be in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate and the lithium nitrate one or several arbitrarily than mixture.
Contain ferro-compound described in the steps A and be in ferrous oxalate, ferrous acetate, ferrous oxide and the ferrous nitrate one or several arbitrarily than mixture.
Phosphorus-containing compound described in the steps A be in diammonium hydrogen phosphate, ammonium dihydrogen phosphate and the ammonium phosphate one or several arbitrarily than mixture.
Fluorochemical described in the steps A be in lithium fluoride, ammonium fluoride, sodium fluoride and the potassium fluoride one or several arbitrarily than mixture.
Ball milling described in the steps A use the chemical pure organic solvent as in methyl alcohol, ethanol, acetone, isopropyl alcohol and the ethyl acetate one or several arbitrarily than mixture.
Described slumpability gas is nitrogen or argon gas.
Described mobile reducing gas is a hydrogen.
Embodiment 12
A, get lithium-containing compound, contain ferro-compound, phosphorus-containing compound and fluorochemical be that the ratio of Li:Fe:P:F=1.02:1:1:0.02 is carried out batch mixing in mol ratio between atom; Every 1mol reactant add the 2000ml ball milling with the chemical pure organic solvent as solvent; Place polytetrafluoroethylene ball grinder ball milling 10 hours, and obtained the presoma suspension-turbid liquid;
B, this presoma suspension-turbid liquid is transported in the spray dryer through measuring pump, under inert gas shielding, carries out drying-granulating, precursor suspension-turbid liquid feed flow is 0.25L/min, and EAT is 208 ℃, and leaving air temp is 114 ℃.
C, the powder that will pass through behind the drying-granulating place tube furnace; Under the protection of slumpability gas or mobile reducing gas; At first the speed with 5 ℃/min is warming up to 386 ℃, constant temperature roast 9 hours, and the speed with 5 ℃/min is warming up to 775 ℃ then; Constant temperature roast 9 hours has obtained anion F
-The ferrous phosphate powder for lithium that mixes is a lithium iron (II) phosphate anode of lithium ion battery material of the present invention.
Preferred version further is:
Lithium-containing compound described in the steps A be in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate and the lithium nitrate one or several arbitrarily than mixture.
Contain ferro-compound described in the steps A and be in ferrous oxalate, ferrous acetate, ferrous oxide and the ferrous nitrate one or several arbitrarily than mixture.
Phosphorus-containing compound described in the steps A be in diammonium hydrogen phosphate, ammonium dihydrogen phosphate and the ammonium phosphate one or several arbitrarily than mixture.
Fluorochemical described in the steps A be in lithium fluoride, ammonium fluoride, sodium fluoride and the potassium fluoride one or several arbitrarily than mixture.
Ball milling described in the steps A use the chemical pure organic solvent as in methyl alcohol, ethanol, acetone, isopropyl alcohol and the ethyl acetate one or several arbitrarily than mixture.
Described slumpability gas is nitrogen or argon gas.
Described mobile reducing gas is a hydrogen.
Embodiment 13
A kind of lithium iron (II) phosphate anode of lithium ion battery material is characterized in that: adopt F
-Anion doped LiFePO 4, the acquisition chemical formula is Li
(1+x)FePO
4F
xThe lithium iron (II) phosphate anode of lithium ion battery material, wherein x is 0.001～0.05; Under the 1C multiplying power first discharge capacity be 135～155mAh/g, circulating after 50 times, discharge capacity is 133～152mAh/g under the 1C multiplying power.
A kind of lithium iron (II) phosphate anode of lithium ion battery preparation methods is characterized in that, comprises following processing step:
A, get lithium-containing compound, contain ferro-compound, phosphorus-containing compound and fluorochemical be Li:Fe:P:F=(1.001～1.05): 1:1 in mol ratio between atom: the ratio of (0.001～0.05) is carried out batch mixing; Every 1mol reactant add 500ml～2500ml ball milling with the chemical pure organic solvent as solvent; Place polytetrafluoroethylene ball grinder ball milling 8～16 hours, and obtained the presoma suspension-turbid liquid;
B, this presoma suspension-turbid liquid is transported in the spray dryer through measuring pump, under inert gas shielding, carries out drying-granulating, precursor suspension-turbid liquid feed flow is 0.05～0.3L/min, and EAT is 200～250 ℃, and leaving air temp is 90～120 ℃.
C, the powder that will pass through behind the drying-granulating place tube furnace; Under the protection of slumpability gas or mobile reducing gas; At first the speed with 5 ℃/min is warming up to 300～450 ℃, constant temperature roast 4～10 hours, and the speed with 5 ℃/min is warming up to 500～800 ℃ then; Constant temperature roast 8～20 hours has obtained anion F
～The ferrous phosphate powder for lithium that mixes is a lithium iron (II) phosphate anode of lithium ion battery material of the present invention.
The lithium-containing compound described in the steps A of the present invention be in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate and the lithium nitrate one or several arbitrarily than mixture.
Contain described in the steps A of the present invention ferro-compound be in ferrous oxalate, ferrous acetate, ferrous oxide and the ferrous nitrate one or several arbitrarily than mixture.
Phosphorus-containing compound described in the steps A of the present invention be in diammonium hydrogen phosphate, ammonium dihydrogen phosphate and the ammonium phosphate one or several arbitrarily than mixture.
Fluorochemical described in the steps A of the present invention be in lithium fluoride, ammonium fluoride, sodium fluoride and the potassium fluoride one or several arbitrarily than mixture.
Ball milling described in the steps A of the present invention use the chemical pure organic solvent as in methyl alcohol, ethanol, acetone, isopropyl alcohol and the ethyl acetate one or several arbitrarily than mixture.
Slumpability gas of the present invention is nitrogen or argon gas, and described mobile reducing gas is a hydrogen.
Claims (9)
1. a lithium iron (II) phosphate anode of lithium ion battery material is characterized in that: adopt F
-Anion doped LiFePO 4, the acquisition chemical formula is Li
(1+x)FePO
4F
xThe lithium iron (II) phosphate anode of lithium ion battery material, wherein x is 0.001～0.05; Under the 1C multiplying power first discharge capacity be 135～155mAh/g, circulating after 50 times, discharge capacity is 133～152mAh/g under the 1C multiplying power.
2. a kind of lithium iron (II) phosphate anode of lithium ion battery preparation methods according to claim 1 is characterized in that, comprises following processing step:
A, get lithium-containing compound, contain ferro-compound, phosphorus-containing compound and fluorochemical be Li:Fe:P:F=(1.001～1.05): 1:1 in mol ratio between atom: the ratio of (0.001～0.05) is carried out batch mixing; Every 1mol reactant add 500ml～2500ml ball milling with the chemical pure organic solvent as solvent; Place polytetrafluoroethylene ball grinder ball milling 8～16 hours, and obtained the presoma suspension-turbid liquid;
B, this presoma suspension-turbid liquid is transported in the spray dryer through measuring pump, under inert gas shielding, carries out drying-granulating, precursor suspension-turbid liquid feed flow is 0.05～0.3L/min, and EAT is 200～250 ℃, and leaving air temp is 90～120 ℃;
C, the powder that will pass through behind the drying-granulating place tube furnace; Under the protection of slumpability gas or mobile reducing gas; At first the speed with 5 ℃/min is warming up to 300～450 ℃, constant temperature roast 4～10 hours, and the speed with 5 ℃/min is warming up to 500～800 ℃ then; Constant temperature roast 8～20 hours has obtained anion F
-The ferrous phosphate powder for lithium that mixes is a lithium iron (II) phosphate anode of lithium ion battery material of the present invention.
3. a kind of lithium iron (II) phosphate anode of lithium ion battery preparation methods according to claim 2 is characterized in that: the lithium-containing compound described in the steps A be in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate and the lithium nitrate one or several arbitrarily than mixture.
4. a kind of lithium iron (II) phosphate anode of lithium ion battery preparation methods according to claim 2 is characterized in that: contain described in the steps A ferro-compound be in ferrous oxalate, ferrous acetate, ferrous oxide and the ferrous nitrate one or several arbitrarily than mixture.
5. a kind of lithium iron (II) phosphate anode of lithium ion battery preparation methods according to claim 2 is characterized in that: phosphorus-containing compound described in the steps A be in diammonium hydrogen phosphate, ammonium dihydrogen phosphate and the ammonium phosphate one or several arbitrarily than mixture.
6. a kind of lithium iron (II) phosphate anode of lithium ion battery preparation methods according to claim 2 is characterized in that: fluorochemical described in the steps A be in lithium fluoride, ammonium fluoride, sodium fluoride and the potassium fluoride one or several arbitrarily than mixture.
7. a kind of lithium iron (II) phosphate anode of lithium ion battery preparation methods according to claim 2 is characterized in that: ball milling described in the steps A use the chemical pure organic solvent as in methyl alcohol, ethanol, acetone, isopropyl alcohol and the ethyl acetate one or several arbitrarily than mixture.
8. a kind of lithium iron (II) phosphate anode of lithium ion battery preparation methods according to claim 2 is characterized in that: described slumpability gas is nitrogen or argon gas.
9. a kind of lithium iron (II) phosphate anode of lithium ion battery preparation methods according to claim 2 is characterized in that: described mobile reducing gas is a hydrogen.
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| CN109192935A (en) * | 2018-07-24 | 2019-01-11 | 佛山市德方纳米科技有限公司 | Anode material for lithium-ion batteries and preparation method thereof |
| CN114933336A (en) * | 2022-06-21 | 2022-08-23 | 宜宾锂宝新材料有限公司 | Fluorine-phosphorus chaperone doped ternary precursor, preparation method thereof and ternary material |
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