CN105731411A - Preparation method of mechanical force chemical activation modified lithium iron phosphate anode material - Google Patents
Preparation method of mechanical force chemical activation modified lithium iron phosphate anode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a mechanical force chemical activation modified lithium iron phosphate anode material. The preparation method comprises the following steps of: primarily uniformly mixing the raw materials including an iron source, a phosphorus source, a lithium source or the lithium source and a carbon source, and carrying out dry method mechanical activation on the mixture. According to the preparation method, a solid-solution-state precursor is obtained by virtue of mechanical chemical activation, each raw material component is continuously extruded, collided and deformed by virtue of high energy, then molecule-level uniform mixing is achieved, particles and crystal particles are relatively small, and the nanoscale powder is obtained, so that the transmission path of lithium ions in the powder is shortened, the multiplying power and the low-temperature performance of the lithium iron phosphate anode material are greatly improved, the discharging gram volume of the lithium iron phosphate anode material at the multiplying power of 15C can reach 133.79mAh/g, and the capacity retention ratio at a low temperature of 20 DEG C can reach above 80%; a wet grinding process and a drying procedure are omitted, so that the energy consumption in the production process is effectively reduced, and the production cost is greatly lowered.
Description
Technical field
The invention belongs to technical field of lithium ion battery positive pole material preparation, particularly relate to a kind of mechanical force and chemical
The preparation method of the LiFePO4 based on activation dry process presoma.
Background technology
LiFePO 4 (LiFePO4), also referred to as LiFePO4, is a kind of novel lithium ion cell positive
Material, have raw material sources extensively, environmental friendliness, safety be high and the advantage such as have extended cycle life, in recent years
It is widely applied at power and energy storage lithium ion battery field.But at electric automobile, automobile starting
The fields such as power supply, low temperature and multiplying power discharging property to lithium iron phosphate positive material require higher, especially vapour
Car starts field of power supplies, it is desirable to lithium iron phosphate positive material can continue at 30C multiplying power discharging, low temperature-20 DEG C
Discharge capacitance is at least more than 70%.
The lithium iron phosphate positive material that produced in conventional processes obtains is existing defects on low temperature and high rate performance,
Reach above-mentioned performance difficulty bigger.The major measure used at present is primary particle nanorize or metal ion is mixed
Miscellaneous, by improving electronic conductivity and the lithium ionic mobility of lithium iron phosphate positive material, improve LiFePO4
The low temperature of positive electrode and high rate performance.But above two method is all under the conditions of aqueous phase or organic facies,
Realized by long-time grinding material.On the one hand, grind for a long time need to consume substantial amounts of electric energy or its
His energy, on the other hand, the material after grinding contains water or organic solvent, needs substantial amounts of energy for will
Water or organic solvent are converted into gaseous state by liquid, and feed separation, thus reach dry purpose, therefore
The energy consumption of above two production method is big, is unfavorable for the energy-saving and cost-reducing of enterprise and cleanly production.
Summary of the invention
In order to overcome the defect of prior art, it is an object of the invention to provide a kind of Mechanochemical Activation and change
Property lithium iron phosphate positive material preparation method, the method use dry process ferric lithium phosphate precursor, need not
Being dried, direct sintering, production procedure is short, and is prone to control of industrialization, and the nano-scale lithium iron phosphate of preparation is just
Pole material has low cost, low temperature and high rate performance advantages of higher.
To achieve these goals, the technical solution used in the present invention is as follows: a kind of Mechanochemical Activation changes
The preparation method of property lithium iron phosphate positive material, including step: with source of iron, phosphorus source, lithium source or phosphorus lithium source and
Carbon source is raw material, after preliminary mixing, mixture is carried out dry method mechanical activation, obtains each component and reach
The precursor of molecular level mixing, predecessor, through a pre-burning, again after bag carbon, obtains through secondary clacining
Nano-scale lithium iron phosphate.
According to above scheme, as anode active material of lithium ion battery.
The preparation method of a kind of Mechanochemical Activation modified phosphate ferrum lithium anode material of the present invention, including such as
Lower concrete steps:
(1) mixing: by source of iron, phosphorus source, lithium source or phosphorus lithium source and carbon source according to mol ratio Fe:P:Li:
C=1:1:(0.9-1.1): (0.2-0.6), tentatively mix in batch mixer；
(2) dry method mechanical activation: the mixture obtained by step (1) is positioned in milling apparatus,
Activation 2-12h, crosses 100 mesh sieves and obtains dry powder predecessor；
(3) pre-burning: by predecessor obtained in step (2), under the protection of noble gas, put into
350-500 DEG C of low temperature calcination 3-6h in kiln, obtains LiFePO4 Preburning material；
(4) secondary bag carbon: the LiFePO4 Preburning material obtained by step (3) is put into batch mixer, presses
Fe:C=1:(0.2-0.6) add carbon source, be uniformly mixed so as to obtain ferric lithium phosphate precursor；
(5) sintering: by ferric lithium phosphate precursor obtained in step (4), in the protection of noble gas
Under, put into and kiln is warming up to 550-700 DEG C is sintered 5-12h, cooling material to 20-100 DEG C,
Obtain the lithium iron phosphate positive material of granule fine uniform, low temperature and good rate capability.
Source of iron described in step (1) is iron phosphate, Ferrox., iron oxide red, high-purity magnet fine mineral powder
In one or more；Described phosphorus source is diammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphate, phosphoric acid
One or more in ferrum；Described lithium source be Lithium hydrate, lithium carbonate, lithium acetate, lithium formate,
One or more in lithium oxalate；Described phosphorus lithium source is lithium phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two
One or more in lithium；Described carbon source be glucose, sucrose, fructose, starch, cellulose,
Citric acid, polypropylene, polyethylene, conductive black, graphite, CNT, carbon nano-fiber, nano-sized carbon
One or more in microsphere；Described batch mixer be V-type batch mixer, conical mixer, inclined mix
One in material machine, three-dimensional material mixer.
Further, the milling apparatus described in step (2) be roller mill, rod mill, double-planet ball mill,
One in vibromill, super micron mill, the described mechanical and chemical activation time is 4-10h.
Further, the noble gas described in step (3) be high-purity argon gas, high pure nitrogen, high-purity helium,
One or more in high-purity neon；Described kiln is roller kilns, tunnel cave, pushed bat kiln, guipure
One in kiln, rotary kiln, clock hood type furnace.
Further, the pre-sinter process in step (3) is: heating rate is 2-10 DEG C/min, holding temperature
For 350-500 DEG C, roasting time is 4-6h, and material is cooled to 20-60 DEG C.
Further, the noble gas described in step (4) be high-purity argon gas, high pure nitrogen, high-purity helium,
One or more in high-purity neon；Described carbon source is glucose, sucrose, fructose, starch, fibre
Dimension element, citric acid, polypropylene, polyethylene, conductive black, graphite, CNT, carbon nano-fiber,
One or more in nano-sized carbon microsphere；Described batch mixer be V-type batch mixer, conical mixer,
One in inclined mixer, three-dimensional material mixer.
Further, the noble gas described in step (5) be high-purity argon gas, high pure nitrogen, high-purity helium,
One or more in high-purity neon；Described kiln is roller kilns, tunnel cave, pushed bat kiln, guipure
One in kiln, rotary kiln, clock hood type furnace.
Further, the sintering process in step (5) is: heating rate is 5-15 DEG C/min, holding temperature
For 550-700 DEG C, roasting time is 5-8h, and material is cooled to 20-80 DEG C.
The preparation method of the present invention, compared with the preparation method of existing lithium iron phosphate positive material, has following
Feature: (1) uses mechanical and chemical activation process to obtain solid solution state predecessor, makes each raw material components under high energy
Constantly extruding, collision, deformation, thus reach the mixing of molecular level so that granule and crystal grain are more tiny,
Obtain nanometer grade powder, thus shorten lithium ion in powder body internal transmission path, be just substantially improved LiFePO4
Pole material multiplying power and cryogenic property, lithium iron phosphate positive material 15C multiplying power discharging gram volume up to
133.79mAh/g ,-20 DEG C of capability retentions of low temperature are up to more than 80%；(2) without wet grinding technique,
Save drying process, effectively reduce the energy consumption in production process, thus be substantially reduced production cost；(3)
Using low temperature presintering technique, make LiFePO4 crystal generate more intact, structure is more stable, particle size
More tiny, uniform, thus improve the chemical property of lithium iron phosphate positive material；(4) two step bags are used
Carbon technique so that granule inside and out can uniform bag carbon, improve the low of lithium iron phosphate positive material
Temperature and high rate performance.
Accompanying drawing explanation
The present invention is further described below in conjunction with the accompanying drawings.
Fig. 1 is the LiFePO4 SEM figure that the embodiment of the present invention 1 produces；
Fig. 2 is the LiFePO4 XRD figure that the embodiment of the present invention 1 produces；
Fig. 3 is 0.2C charging and discharging curve under the LiFePO4 room temperature that the embodiment of the present invention 1 produces；
Fig. 4 is the discharge curve under the LiFePO4 room temperature that the embodiment of the present invention 1 produces under different multiplying.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
(1) weighing 10 kilograms of purity is the FePO of 99%4·2H2O, 2.314 kilograms of purity are 99.5%
LiOH·H2O and 703.52 grams of glucoses are placed in V-type batch mixer mixing 2h；
(2) mixture obtained in step (1) is added mechanical and chemical activation 5h in roller mill, cross 100
Mesh sieve obtains dry powder predecessor；
(3) by obtained by step (2) predecessor put in mesh-belt kiln, in the condition of high pure nitrogen
Under, with the ramp of 2 DEG C/min to 350 DEG C, constant temperature 4h, it is cooled to 30 DEG C, obtains Preburning material；
(4) Preburning material obtained in step (3) and 222.54 grams of polypropylene are mixed in inclined mixer
Close 1h；
(5) mixture obtained in step (4) is placed in mesh-belt kiln, under conditions of high pure nitrogen,
With the ramp of 5 DEG C/min to 650 DEG C, constant temperature 6h, material is cooled to 30 DEG C in kiln, can after taking-up
Obtain the lithium iron phosphate positive material of the present invention.
As it is shown in figure 1, the lithium iron phosphate positive material of the present embodiment synthesis is crystallization through X-ray diffraction analysis
Intact LiFePO4Pure phase, the carbon-coating of parcel presents with amorphous structure；As in figure 2 it is shown, the present embodiment
The SEM photograph of the lithium iron phosphate positive material of synthesis shows, LiFePO 4 material primary particle prepared by this method
For 50-200nm, crystal grain is tiny, uniform.
Lithium iron phosphate positive material the above embodiment of the present invention obtained is prepared as lithium ion cell positive assembling
CR2025 type button cell is become to carry out electrochemical property test: (i.e. the present invention provides by positive active material
LiFePO 4 material), acetylene black, Kynoar (PVDF) 75:15:10 in mass ratio mixing stir
Mix 4h, uniformly slip, slip is coated in uniformly a diameter of 1mm, thickness is the aluminum of 0.3mm
On sheet, in vacuum drying oven, 100 DEG C of drying, make positive pole；Negative electricity extremely metal lithium sheet, barrier film is
Celgard-2325, electrolyte is the ethylene carbonate (EC) of the equal-volume ratio of 1M LiPF6, dimethyl carbon
Acid esters (DEC) solution.The vacuum glove box being assemblied in full argon of battery is carried out, constant current charge and discharge
The voltage range of electrical testing is 2.0～4.0V, and discharge and recharge system calculates according to the theoretical capacity of 170mAh/g,
I.e. 1C is 170mA/g.Multiplying power testing scheme is: use 1C charging, respectively with 1C, 3C, 5C, 10C
Discharging with 15C, test process is carried out at room temperature 25 DEG C.Low-temperature test scheme is: in room temperature 25
At DEG C, battery is charged with 0.2C, then constant temperature 12h at-20 DEG C in high/low temperature test cabinet, then-20
Discharge with 0.2C at DEG C.
Fig. 3 is the 0.2C first charge-discharge curve of the LiFePO4 respective battery that embodiment 1 prepares, table
Bright material discharging platform is smooth, good reversibility, and 0.2C electric discharge gram volume is 157.78mAh/g.
As shown in Figure 4, the lithium iron phosphate positive material that embodiment 1 prepares is at 1C, 3C, 5C, 10C
With gram volume under 15C discharge-rate be followed successively by 153.79mAh/g, 151.88mAh/g, 149.64mAh/g,
144.28mAh/g and 133.79mAh/g.
At the lithium iron phosphate positive material that embodiment 1 prepares-20 DEG C, 0.2C electric discharge gram volume is
128.35mAh/g, for the 81.35% of normal temperature condition discharge capacity.
Embodiment 2
(1) weighing 10 kilograms of purity respectively is the FePO of 99%4·2H2O, 3.657 kilograms of purity are 99%
CH3COOLi and 856.04 grams of sucrose are placed in conical mixer mixing 2h；
(2) mixture obtained in step (1) is added mechanical and chemical activation 5h in super micron mill,
Cross 100 mesh sieves and obtain dry powder predecessor；
(3) predecessor obtained in step (2) is put in roller kilns, under conditions of high-purity argon gas,
With the ramp of 2 DEG C/min to 400 DEG C, constant temperature 4h, it is cooled to 30 DEG C, obtains Preburning material；
(4) Preburning material obtained in step (3) and 196.65 grams of polypropylene are mixed in conical mixer
Close 1h；
(5) mixture obtained in step (4) is placed in roller kilns, under conditions of high-purity argon gas,
With the ramp of 5 DEG C/min to 650 DEG C, constant temperature 6h, material is cooled to 30 DEG C in kiln, can after taking-up
Obtain the lithium iron phosphate positive material of the present invention.
The lithium iron phosphate positive material that embodiment 2 prepares, 0.2C electric discharge gram volume is 154.33mAh/g,
Under 1C, 3C, 5C, 10C and 15C discharge-rate gram volume be followed successively by 150.68mAh/g,
148.75mAh/g, 146.46mAh/g, 140.38mAh/g and 129.74mAh/g.
At the lithium iron phosphate positive material that embodiment 2 prepares-20 DEG C, 0.2C electric discharge gram volume is
124.45mAh/g, for the 80.64% of normal temperature condition discharge capacity.
Embodiment 3
(1) weighing 10 kilograms of purity is the FePO of 99%4·2H2O, 2.038 kilograms of purity are 99.5%
Li2CO3Mixing 1.5h it is placed in three-dimensional material mixer with 467.2 grams of citric acids；
(2) mixture obtained in step (1) is added mechanical and chemical activation 6h in rod mill, cross 100
Mesh sieve obtains dry powder predecessor；
(3) by obtained by step (2) predecessor put in clock hood type furnace, in the condition of high-purity argon gas
Under, with the ramp of 2 DEG C/min to 400 DEG C, constant temperature 4h, it is cooled to 30 DEG C, obtains Preburning material；
(4) Preburning material obtained in step (3) and 192.67 grams of graphite are mixed in V-type batch mixer
2h；
(5) mixture obtained in step (4) is placed in clock hood type furnace, under conditions of high-purity argon gas,
With the ramp of 5 DEG C/min to 650 DEG C, constant temperature 6h, material is cooled to 30 DEG C in kiln, can after taking-up
Obtain the lithium iron phosphate positive material of the present invention.
The lithium iron phosphate positive material that embodiment 3 prepares, 0.2C electric discharge gram volume is 152.49mAh/g,
Under 1C, 3C, 5C, 10C and 15C discharge-rate gram volume be followed successively by 147.39mAh/g,
142.96mAh/g, 138.46mAh/g, 122.31mAh/g and 111.77mAh/g.
At the lithium iron phosphate positive material that embodiment 3 prepares-20 DEG C, 0.2C electric discharge gram volume is
107.63mAh/g, for the 70.58% of normal temperature condition discharge capacity.
Embodiment 4
(1) weighing 9.48 kilograms of purity is the FeC of 99%2O4·2H2O, 2.825 kilograms of purity are 99%
Li2C2O4, 6.094 kilograms of purity be the NH of 99%4H2PO4It is placed in tiltedly with 254.58 grams of conductive blacks
Formula batch mixer mixes 2h；
(2) mixture obtained in step (1) is added mechanical and chemical activation 7h in vibromill, cross 100
Mesh sieve obtains dry powder predecessor；
(3) by obtained by step (2) predecessor put in clock hood type furnace, in the condition of high-purity argon gas
Under, with the ramp of 2 DEG C/min to 350 DEG C, constant temperature 5h, it is cooled to 30 DEG C, obtains Preburning material；
(4) Preburning material obtained in step (3) and 222.54 grams of polypropylene are mixed in inclined mixer
Close 2h；
(5) mixture obtained in step (4) is placed in pusher furnace, in the condition of high pure nitrogen gas
Under, with the ramp of 5 DEG C/min to 700 DEG C, constant temperature 8h, material is cooled to 30 DEG C in kiln, takes out
The lithium iron phosphate positive material of the rear available present invention.
The lithium iron phosphate positive material that embodiment 4 prepares, 0.2C electric discharge gram volume is 155.44mAh/g,
Under 1C, 3C, 5C, 10C and 15C discharge-rate gram volume be followed successively by 151.86mAh/g,
149.65mAh/g, 147.52mAh/g, 141.64mAh/g and 130.38mAh/g.
At the lithium iron phosphate positive material that embodiment 4 prepares-20 DEG C, 0.2C electric discharge gram volume is
125.55mAh/g, for the 80.77% of normal temperature condition discharge capacity.
Embodiment 5
(1) weighing 8.48 kilograms of purity is the Fe of 99.8%2O3, 5.712 kilograms of purity be 99.9%
LiH2PO4Mixing 2h it is placed in V-type batch mixer with 572.24 grams of starch；
(2) mixture obtained in step (1) is added mechanical and chemical activation 8h in double-planet ball mill,
Cross 100 mesh sieves and obtain dry powder predecessor；
(3) by obtained by step (2) predecessor put in rotary kiln, in the condition of high pure nitrogen
Under, with the ramp of 2 DEG C/min to 500 DEG C, constant temperature 4h, it is cooled to 30 DEG C, obtains Preburning material；
(4) Preburning material obtained in step (3) and 192.67 grams of graphite are mixed in V-type batch mixer
2h；
(5) mixture obtained in step (4) is placed in pusher furnace, under conditions of high pure nitrogen,
With the ramp of 5 DEG C/min to 700 DEG C, constant temperature 8h, material is cooled to 30 DEG C in kiln, can after taking-up
Obtain the lithium iron phosphate positive material of the present invention.
The lithium iron phosphate positive material that embodiment 5 prepares, 0.2C electric discharge gram volume is 152.49mAh/g,
Under 1C, 3C, 5C, 10C and 15C discharge-rate gram volume be followed successively by 145.34mAh/g,
140.81mAh/g, 136.45mAh/g, 120.18mAh/g and 109.64mAh/g.
At the lithium iron phosphate positive material that embodiment 5 prepares-20 DEG C, 0.2C electric discharge gram volume is
104.86mAh/g, for the 68.77% of normal temperature condition discharge capacity.
Claims (9)
1. the preparation method of a Mechanochemical Activation modified phosphate ferrum lithium anode material, it is characterised in that
Including step: with source of iron, phosphorus source, lithium source or phosphorus lithium source and carbon source as raw material, after preliminary mixing, will
Mixture carries out dry method mechanical activation, obtains each component and reaches the precursor of molecular level mixing, and predecessor passes through
Pre-burning, again after bag carbon, obtains nano-scale lithium iron phosphate through secondary clacining.
The preparation side of Mechanochemical Activation modified phosphate ferrum lithium anode material the most according to claim 1
Method, it is characterised in that comprise the following specific steps that:
(1) mixing: by source of iron, phosphorus source, lithium source or phosphorus lithium source and carbon source according to mol ratio Fe:P:Li:
C=1:1:(0.9-1.1): (0.2-0.6), tentatively mix in batch mixer；
(2) dry method mechanical activation: the mixture obtained by step (1) is positioned in milling apparatus,
Activation 2-12h, crosses 100 mesh sieves and obtains dry powder predecessor；
(3) pre-burning: by predecessor obtained in step (2), under the protection of noble gas, put into
350-500 DEG C of low temperature calcination 3-6h in kiln, obtains LiFePO4 Preburning material；
(4) secondary bag carbon: the LiFePO4 Preburning material obtained by step (3) is put into batch mixer, presses
Fe:C=1:(0.2-0.6) carbon source is added, mixing；
(5) sintering: by mixture obtained in step (4), under the protection of noble gas, put into
Being warming up to 550-700 DEG C in kiln and be sintered 5-12h, cooling material, to 20-100 DEG C, i.e. can get granule
The lithium iron phosphate positive material of fine uniform, low temperature and good rate capability.
The system of Mechanochemical Activation modified phosphate ferrum lithium anode material the most according to claim 1 and 2
Preparation Method, it is characterised in that described source of iron is iron phosphate, Ferrox., iron oxide red, high pure magnetic iron
One or more in fine ore；Described phosphorus source be diammonium phosphate, ammonium dihydrogen phosphate, ammonium phosphate,
One or more in iron phosphate；Described lithium source is Lithium hydrate, lithium carbonate, lithium acetate, formic acid
One or more in lithium, lithium oxalate；Described phosphorus lithium source is lithium phosphate, lithium dihydrogen phosphate, phosphoric acid
One or more in hydrogen two lithium；Described carbon source is glucose, sucrose, fructose, starch, fiber
Element, citric acid, polypropylene, polyethylene, conductive black, graphite, CNT, carbon nano-fiber, receive
Rice carbosphere in one or more；Described batch mixer is V-type batch mixer, conical mixer, tiltedly
One in formula batch mixer, three-dimensional material mixer.
The preparation side of Mechanochemical Activation modified phosphate ferrum lithium anode material the most according to claim 2
Method, it is characterised in that the milling apparatus described in step (2) is roller mill, rod mill, double-planet ball milling
One in machine, vibromill, super micron mill, the described mechanical and chemical activation time is 3-12h.
The preparation side of Mechanochemical Activation modified phosphate ferrum lithium anode material the most according to claim 2
Method, it is characterised in that the noble gas described in step (3) is high-purity argon gas, high pure nitrogen, high-pure helium
One or more in gas, high-purity neon；Described kiln be roller kilns, tunnel cave, pushed bat kiln,
One in mesh-belt kiln, rotary kiln, clock hood type furnace.
The preparation side of Mechanochemical Activation modified phosphate ferrum lithium anode material the most according to claim 2
Method, it is characterised in that the pre-sinter process in step (3) is: heating rate is 2-10 DEG C/min, insulation temperature
Degree is for 350-500 DEG C, and roasting time is 4-6h, and material is cooled to 20-60 DEG C.
The preparation side of Mechanochemical Activation modified phosphate ferrum lithium anode material the most according to claim 2
Method, it is characterised in that the noble gas described in step (4) is high-purity argon gas, high pure nitrogen, high-pure helium
One or more in gas, high-purity neon；Described carbon source be glucose, sucrose, fructose, starch,
Cellulose, citric acid, polypropylene, polyethylene, conductive black, graphite, CNT, carbon nano-fiber,
One or more in nano-sized carbon microsphere；Described batch mixer be V-type batch mixer, conical mixer,
One in inclined mixer, three-dimensional material mixer.
The preparation side of Mechanochemical Activation modified phosphate ferrum lithium anode material the most according to claim 2
Method, it is characterised in that the noble gas described in step (5) is high-purity argon gas, high pure nitrogen, high-pure helium
One or more in gas, high-purity neon；Described kiln be roller kilns, tunnel cave, pushed bat kiln,
One in mesh-belt kiln, rotary kiln, clock hood type furnace.
The preparation side of Mechanochemical Activation modified phosphate ferrum lithium anode material the most according to claim 2
Method, it is characterised in that the sintering process in step (5) is: heating rate is 5-15 DEG C/min, insulation temperature
Degree is for 550-700 DEG C, and roasting time is 5-8h, and material is cooled to 20-80 DEG C.
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