CN102664262A - Method for preparing lithium ferrous silicate or carbon ferrous silicate cathode material for lithium ion battery - Google Patents
Method for preparing lithium ferrous silicate or carbon ferrous silicate cathode material for lithium ion battery Download PDFInfo
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Abstract
The invention discloses a method for preparing a lithium ferrous silicate or carbon ferrous silicate cathode material for a lithium ion battery, relates to a method for preparing a cathode material for a lithium ion battery and aims to solve the problems that the conventional prepared lithium ferrous silicate or carbon ferrous silicate composite is low in purity, inhomogeneous in granularity, and poor in electrochemical cycling stability. The method comprises the following steps of: 1, weighing a lithium salt compound, a ferric salt compound, a nano silica and a carbon source compound; 2, dispersing the weighed materials in the step 1 into a dispersing agent by a ball mill or ultrasonic dispersion method to obtain mixed liquor; 3, drying the mixed liquor by a spray drying method to obtain precursor powder; and 4, heating, namely heating the precursor powder obtained in the step 3 under the protection of inert gas in a certain flow rate, cooling naturally to room temperature, and thus obtaining the lithium ferrous silicate or carbon ferrous silicate cathode material for the lithium ion battery. The method is mainly applied to preparation of the lithium ferrous silicate or carbon ferrous silicate cathode material for the lithium ion battery.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium ion battery.
Background technology
Along with the progress and the science and technology development of human society, make face of mankind two hang-ups, the one, the minimizing day by day of non-renewable resources such as coal, oil, natural gas; The 2nd, the environmental problem that the mankind depend on for existence becomes increasingly conspicuous.Therefore it is extremely urgent to develop pollution-free, non-harmful new energy technology.Since lithium ion battery industrialization based on lithium cobaltate cathode, lithium ion battery with its high-energy-density, high discharge voltage, specific capacity is big, self-discharge rate is low, memory-less effect and advantage such as pollution-free receive the extensive concern of countries in the world.The iron of exploitation is positive electrode in recent years, because of it has aboundresources, low price, nontoxic, environmental friendliness, Heat stability is good, completeness advantages of higher, has also obtained broad research.The iron of report is that positive electrode mainly is LiFePO 4 (LiFePO at present
4) and ferrosilicon silicate of lithium (Li
2FeSiO
4), because element silicon content the first in the element on earth all is safe from harm to the environment and the mankind, and Li
2FeSiO
4With respect to LiFePO
4Have cost of material cheaper, with advantages such as the compatibility of environment is better, in addition from Li
2FeSiO
4Say 1mol Li on the molecular formula
2FeSiO
4Can embedding/taking off the 2mol lithium ion, this just means may obtain to compare LiFePO
4Bigger capacity, so Li
2FeSiO
4Be expected to become low cost, the high performance lithium ion battery anode material of a new generation.
Orthosilicate Li
2FeSiO
4Have and low temperature li
3PO
4Similar structure belongs to rhombic system, and wherein oxygen atom is arranged with the tightly packed mode of positive tetrahedron, and Fe and Si are in oxygen atom tetrahedron center separately.At present, the Li of bibliographical information
2FeSiO
4Typical preparation method have that high temperature solid-state is synthetic, sol-gel process and hydro thermal method etc.At " Electrochemical performance of Li
2FeSiO
4As a new Li-battery cathode material " (author: be raw material through high temperature solid-state method with lithium metasilicate, ferrous oxalate and tetraethoxysilane A.Nyten etc.), mix the back at CO/CO
2The following 750 ℃ of reaction 24h high temperature of atmosphere have synthesized Li
2FeSiO
4/ C composite material, synthetic Li
2FeSiO
4/ C composite material discharges and recharges at 2.0～3.7V with the 1/16C electric current at 60 ℃, and discharge capacity is 130mAh/g.At " Impact of synthesis conditions on the structure and performance of Li
2FeSiO
4" (author: R.Dominko etc.) silicon dioxide is dispersed in lithium hydroxide solution through ultrasonic assisting; Mix with solution of ferrous chloride then; More than 150 ℃ of isothermal reaction 72h, the powder that obtains is used the distilled water cyclic washing under Ar atmosphere, obtain Li after the drying in airtight autoclave
2FeSiO
4Powder, but the material electrochemical performance that obtains is relatively poor, discharges and recharges at 2.0～4.2V with 1/30C multiplying power electric current under the room temperature, and reversible capacity is about 91mAh/g.At " Structure and electrochemical performance of Li
2MnSiO
4And Li
2FeSiO
4As potential Li-battery cathode materials " (author: R.Dominko etc.) with mixture, the CH of ironic citrate, ferric nitrate
3COOLi and SiO
2Powder is a raw material, in ultrasonic water bath, prepares gel, through dry, grinds the back in obtaining Li behind the reaction 1h under 700 ℃ the inert atmosphere
2FeSiO
4, the Li that obtains
2FeSiO
4At 60 ℃, discharge and recharge at 2.0～3.8V with the 1/20C electric current, reversible capacity is about 110mAh/g.At application number is open in 201010148354.2 the Chinese patent " a kind of preparation method of lithium ion battery ferric metasilicate lithium positive electrode material ": 2: 1: 1 the ratio of mol ratio according to Li: Fe: Si is mixed basic material Li source compound, Fe source compound and silicon dioxide; And the adding quality accounts for the thermal conducting agent of above-mentioned basic material gross mass 2%-40%; Material after grinding is pressed into bulk after drying; Put into the crucible that active carbon is housed; Again crucible is placed the microwave radiation heating 2-30 minute, can make ferric metasilicate lithium positive electrode material.At application number is open in 201010280398.0 the Chinese patent " a kind of high performance lithium ion battery is with ferrous silicate lithium anode material and preparation method thereof ": material is a raw material with lithium source, source of iron, silicon source and carbon source; And make Li: Fe: the mol ratio of Si is (1.98-2.05): (0.98-1.02): 1, and the carbon source volume is the 1-30% of lithium source, source of iron, the three kinds of mixture of substances gross masses in silicon source.Take by weighing lithium source, source of iron, silicon source and carbon source respectively by above-mentioned mol ratio and addition ratio, the silicon source is pulverized and is scattered in the water, stir with ultrasonic and become suspension, source of iron and lithium source is water-soluble, stirring and ultrasonic, the adding reducing agent is with Fe in the solution
3+Be reduced into Fe
2+, pour the suspension of silicon salt in source of iron and the lithium source solution into, add carbon source and mixing behind the mixing again, under inert gas shielding, above-mentioned solution is distilled to solvent volatilizees fully, process through oven dry, compacting, roasting technique.
Traditional high temperature solid phase synthesis needs higher synthesis temperature; Obtain material grains and particle is big; Be unfavorable for the raising of ferrosilicon silicate of lithium chemical property; And hydro thermal method, microwave method, sol-gel process are difficult to industrial applications, and it is low to obtain powder body material density, is unfavorable for improving the volume of battery energy density.Therefore, research and development have the Li of good electrical chemical property and higher density concurrently
2FeSiO
4The preparation method of/C positive electrode is for promoting Li
2FeSiO
4The research and development of/C positive electrode and industrialization process promote the development of lithium ion battery, electric motor car and related industry that significance is arranged.
Summary of the invention
The ferrous metasilicate lithium/carbon composite material that the objective of the invention is to solve existing preparation exists that purity is low, the problem of granularity heterogeneity and electrochemistry cyclical stability difference, and the preparation method of a kind of lithium ion battery with ferrosilicon silicate of lithium/carbon positive electrode is provided.
A kind of lithium ion battery is with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode; Specifically accomplish according to the following steps: one, weighing: at first according to Li: the mol ratio of Fe: Si is (1.9～2.1): (0.95～1.05): 1 takes by weighing lithium salt compound, molysite compound and nano silicon, takes by weighing carbon-source cpd by 0.1%～25% of lithium salt compound, molysite compound and nano silicon gross mass then; Two, disperse: with deionized water or water-ethanol solution is decentralized medium; The lithium salt compound, molysite compound, nano silicon and the carbon-source cpd that adopt ball grinding method or ultra-sonic dispersion method that step 1 is taken by weighing are scattered in deionized water or the water-ethanol solution; Jitter time is 0.5h～3h, obtains mixed liquor; Three, adopt spray drying process that mixed liquor is carried out drying, promptly obtain precursor powder; Four, heat treated: at flow velocity is that the precursor powder that under the inert gas shielding of 100mL/min～5000mL/min step 3 is obtained carries out heat treated; Be that 1 ℃/min～20 ℃/min is warming up to 300 ℃～450 ℃ from room temperature at first with heating rate; And at 300 ℃～450 ℃ following heat treated 0.5h～3h; Continuing then with heating rate is that 1 ℃/min～20 ℃/min is warming up to 500 ℃～750 ℃; And 500 ℃～750 ℃ following heat treated 1h～24h, naturally cool to room temperature then, promptly obtain lithium ion battery with ferrosilicon silicate of lithium/carbon positive electrode.
Advantage of the present invention: one, raw materials mix of the present invention adopts the raw material of solid-liquid combination, and the uniformity of raw materials mix is improved greatly; Two, the present invention adopts the method that ball grinding method or ultra-sonic dispersion method and spray drying combine; With presoma pulverize, evenly mixing, rapid draing and be controlled to uniform spherical; The flowability of material when helping the tap density that keeps the uniform admixture of raw material, improves product material and preparing slurry, the second particle particle size distribution of gained ferrous metasilicate lithium/carbon composite material is 0.5 μ m～15 μ m; Three, the lithium ion battery of the present invention's preparation is with ferrosilicon silicate of lithium/carbon positive electrode particle is tiny, even, spherical in shape, purity is high, energy density is high, the stable circulation performance is good; Has good conductivity; Cycle performance and higher charge/discharge capacity, and be more than the 150mAh/g with 1C rate charge-discharge specific capacity; So the lithium ion battery of the present invention's preparation has very high practical value, is with a wide range of applications as cell positive material with ferrosilicon silicate of lithium/carbon positive electrode.
Embodiment
Embodiment one: this execution mode is the preparation method of a kind of lithium ion battery with ferrosilicon silicate of lithium/carbon positive electrode, specifically accomplishes according to the following steps:
One, weighing: at first according to Li: the mol ratio of Fe: Si is (1.9～2.1): (0.95～1.05): 1 takes by weighing lithium salts, ferrous salt and nano silicon, takes by weighing organic carbon source by 1%～30% of lithium source, source of iron and nano silicon gross mass then; Two, disperse: with deionized water or water-ethanol solution is decentralized medium; The lithium salts, ferrous salt, nano silicon and the organic carbon source that adopt ball grinding method or ultra-sonic dispersion method that step 1 is taken by weighing are scattered in deionized water or the water-ethanol solution; Jitter time is 0.5h～3h, obtains mixed liquor; Three, adopt spray drying process that mixed liquor is carried out drying, promptly obtain precursor powder; Four, heat treated: at flow velocity is that the precursor powder that under the inert gas shielding of 100mL/min～5000mL/min step 3 is obtained carries out heat treated; Be that 1 ℃/min～20 ℃/min is warming up to 300 ℃～450 ℃ from room temperature at first with heating rate; And at 300 ℃～450 ℃ following heat treated 0.5h～3h; Continuing then with heating rate is that 1 ℃/min～20 ℃/min is warming up to 700 ℃～900 ℃; And 700 ℃～900 ℃ following heat treated 1h～24h, naturally cool to room temperature then, promptly obtain lithium ion battery with ferrosilicon silicate of lithium/carbon positive electrode.
This execution mode raw materials mix adopts the raw material of solid-liquid combination, and the uniformity of raw materials mix is improved greatly.
This execution mode adopts ball grinding method or ultra-sonic dispersion method and spray-dired method; With presoma pulverize, evenly mixing, rapid draing and be controlled to uniform spherical; The flowability of material when helping the tap density that keeps the uniform admixture of raw material, improves product material and preparing slurry, the second particle particle size distribution of gained ferrous metasilicate lithium/carbon composite material is 0.5 μ m～15 μ m.
The lithium ion battery of the present invention's preparation is with ferrosilicon silicate of lithium/carbon positive electrode particle is tiny, even, spherical in shape, purity is high, energy density is high, the stable circulation performance is good; Has good conductivity; Cycle performance and higher charge/discharge capacity, and be more than the 150mAh/g with 1C rate charge-discharge specific capacity; So the lithium ion battery of the present invention's preparation has very high practical value, is with a wide range of applications as cell positive material with ferrosilicon silicate of lithium/carbon positive electrode.
Embodiment two: this execution mode with the difference of embodiment one is: lithium salt compound described in the step 1 is selected from lithium metasilicate, lithium metasilicate, lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium chloride, lithium nitrate and lithium phosphate.Other are identical with embodiment one.
Embodiment three: this execution mode with one of embodiment one or two difference is: the compound of molysite described in the step 1 is selected from ferrous oxalate, ferrous acetate, frerrous chloride and ferrous phosphate.Other are identical with embodiment one or two.
Embodiment four: this execution mode with one of embodiment one to three difference is: the particle diameter of nanometer silicon dioxide particle described in the step 1 is less than 35nm.Other are identical with embodiment one to three.
Embodiment five: this execution mode with one of embodiment one to four difference is: carbon-source cpd described in the step 1 is selected from sucrose, glucose, fructose, citric acid, phenolic resins, coal tar asphalt, petroleum asphalt and starch.Other are identical with embodiment one to four.
Embodiment six: one of this execution mode and embodiment one to five difference is: the ball grinding method concrete operations described in the step 2 are following: at first according to ball material mass ratio (18～20): 1 lithium salt compound, molysite compound, nano silicon and carbon-source cpd mixing that ball milling ball and step 1 are taken by weighing; Add water or water-ethanol solution then as dispersant; And be ball milling 0.5h～3h under 200rpm～400rpm at rotational speed of ball-mill, promptly obtain mixed liquor after isolating the ball milling ball; The quality of the dispersant of said adding is (5～8) with the ratio of lithium salt compound, molysite compound, nano silicon and carbon-source cpd gross mass that step 1 takes by weighing: 1.Other are identical with embodiment one to five.
Embodiment seven: this execution mode with one of embodiment one to six difference is: the ultra-sonic dispersion method concrete operations described in the step 2 are following: the lithium salt compound that at first step 1 is taken by weighing, molysite compound, nano silicon and carbon-source cpd join in the water or water-ethanol solution as dispersant; Be ultrasonic auxiliary ultrasonic dispersion 0.5h～3h down of 80kHz～100kHz in frequency then, promptly obtain mixed liquor; The quality of described dispersant is (5～10) with the ratio of lithium salt compound, molysite compound, nano silicon and carbon-source cpd gross mass that step 1 takes by weighing: 1.Other and embodiment one to six phase are together.
Embodiment eight: this execution mode with one of embodiment one to seven difference is: the volume ratio of deionized water and ethanol is (0.2～1.8) in the water-ethanol solution described in the step 2: 1.Other are identical with embodiment one to seven.
Embodiment nine: this execution mode with one of embodiment one to eight difference is: the spray drying process concrete operations described in the step 3 are following: the water or the water-ethanol mixed solution that at first will in the mixed liquor of step 2 preparation, add as diluent dilute; Being diluted to total cation concentration is 0.1mol/L～1mol/L, is that 0.5L/min～10L/min, inlet temperature are 200 ℃～300 ℃ N in charging rate then
2Or carrying out spray drying under the Ar protection, the volume ratio of deionized water and ethanol is (0.2～1.8) in the described water-ethanol solution: 1.Other are identical with embodiment one to eight.
Embodiment ten: one of this execution mode and embodiment one to nine difference is: the inert gas described in the step 4 is nitrogen, argon gas, hydrogen-nitrogen mixed gas or hydrogen-argon-mixed; The volume content of hydrogen is 0.5%～10% in wherein said hydrogen-nitrogen mixed gas, and the volume content of wherein said hydrogen-argon-mixed middle hydrogen is 0.5%～10%.Other are identical with embodiment one to nine.
Adopt subordinate's experimental verification effect of the present invention:
Test one: a kind of lithium ion battery is specifically accomplished with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode according to the following steps:
One, weighing: at first according to Li: the mol ratio of Fe: Si is to take by weighing lithium carbonate, ferrous oxalate and nano silicon at 2: 1: 1, takes by weighing sucrose by 20% of lithium carbonate, ferrous oxalate and nano silicon gross mass then; Two, disperse: with water-ethanol solution is decentralized medium, and the lithium carbonate, ferrous oxalate, nano silicon and the sucrose that adopt ball grinding method that step 1 is taken by weighing are scattered in the water-ethanol solution, and jitter time is 2h, obtains mixed liquor; Three, adopt spray drying process that mixed liquor is carried out drying, promptly obtain precursor powder; Four, heat treated: at flow velocity is that the precursor powder that under the Ar protection of 2000mL/min step 3 is obtained carries out heat treated; Be that 10 ℃/min is warming up to 350 ℃ from room temperature at first with heating rate; And at 350 ℃ of following heat treated 2h, continuing then with heating rate is that 10 ℃/min is warming up to 700 ℃, and 700 ℃ of following heat treated 10h; Naturally cool to room temperature then, promptly obtain lithium ion battery with ferrosilicon silicate of lithium/carbon positive electrode.
The nanometer silicon dioxide particle particle diameter is less than 35nm described in this test procedure one.
Ball grinding method concrete operations described in this test procedure two are following: the lithium carbonate, ferrous oxalate, nano silicon and the sucrose mixing that at first according to ratio of grinding media to material 19: 1 ball milling ball and step 1 are taken by weighing; Add water-ethanol solution then as dispersant; And be ball milling 2h under the 200rpm at rotational speed of ball-mill, promptly obtain mixed liquor after isolating the ball milling ball; The quality of the dispersant of said adding is 6.5: 1 with the ratio of lithium carbonate, ferrous oxalate, nano silicon and sucrose gross mass that step 1 takes by weighing; The volume ratio of deionized water and ethanol is 1: 1 in the water-ethanol solution described in this test procedure two.
Spray drying process concrete operations described in this test procedure three are following: the water-ethanol mixed solution that at first will in the mixed liquor of step 2 preparation, add as diluent dilutes; Being diluted to total cation concentration is 0.5mol/L; Be that 5L/min, inlet temperature are to carry out spray drying under 250 ℃ the Ar protection in charging rate then, the volume ratio of deionized water and ethanol is 1: 1 in the described water-ethanol solution.
Adopt lithium ion battery to use ferrosilicon silicate of lithium/carbon positive electrode to be positive pole, the lithium sheet is that negative pole is assembled into the R2025 button cell, is 155mAh/g through the specific discharge capacity that detects under the 0.1C multiplying power.
Test two: a kind of lithium ion battery is specifically accomplished with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode according to the following steps:
One, weighing: at first according to Li: the mol ratio of Fe: Si is to take by weighing lithium hydroxide, ferrous oxalate and nano silicon at 2: 1: 1, takes by weighing citric acid by 15% of lithium hydroxide, ferrous oxalate and nano silicon gross mass then; Two, disperse: with water-ethanol solution is decentralized medium, and the lithium hydroxide, ferrous oxalate, nano silicon and the citric acid that adopt ball grinding method that step 1 is taken by weighing are scattered in the water-ethanol solution, and jitter time is 2h, obtains mixed liquor; Three, adopt spray drying process that mixed liquor is carried out drying, promptly obtain precursor powder; Four, heat treated: at flow velocity is the N of 2000mL/min
2The precursor powder that protection obtains step 3 down carries out heat treated; Be that 5 ℃/min is warming up to 350 ℃ from room temperature at first with heating rate; And at 350 ℃ of following heat treated 2h, continuing then with heating rate is that 5 ℃/min is warming up to 700 ℃, and 700 ℃ of following heat treated 10h; Naturally cool to room temperature then, promptly obtain lithium ion battery with ferrosilicon silicate of lithium/carbon positive electrode.
The nanometer silicon dioxide particle particle diameter is less than 35nm described in this test procedure one.
Ball grinding method concrete operations described in this test procedure two are following: the lithium hydroxide, ferrous oxalate, nano silicon and the citric acid mixing that at first according to ratio of grinding media to material 19: 1 ball milling ball and step 1 are taken by weighing; Add water-ethanol solution then as dispersant; And be ball milling 2h under the 200rpm at rotational speed of ball-mill, promptly obtain mixed liquor after isolating the ball milling ball; The quality of the dispersant of said adding is 6.5: 1 with the ratio of lithium hydroxide, ferrous oxalate, nano silicon and citric acid gross mass that step 1 takes by weighing; The volume ratio of deionized water and ethanol is 1: 1 in the water-ethanol solution described in this test procedure two.
Spray drying process concrete operations described in this test procedure three are following: the water-ethanol mixed solution that at first will in the mixed liquor of step 2 preparation, add as diluent dilutes; Being diluted to total cation concentration is 0.5mol/L, is that 5L/min, inlet temperature are 250 ℃ N in charging rate then
2Carry out spray drying under the protection, the volume ratio of deionized water and ethanol is 1: 1 in the described water-ethanol solution.
Adopting the lithium ion battery of this test preparation to use ferrosilicon silicate of lithium/carbon positive electrode to be assembled into the R2025 button cell for anodal and lithium sheet as negative pole, is 148mAh/g through the specific discharge capacity that detects under the 0.1C multiplying power.
Test three: a kind of lithium ion battery is specifically accomplished with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode according to the following steps:
One, weighing: at first according to Li: the mol ratio of Fe: Si is to take by weighing lithium metasilicate, ferrous oxalate and nano silicon at 2: 1: 1, takes by weighing sucrose by 25% of lithium metasilicate, ferrous oxalate and nano silicon gross mass then; Two, disperse: with water-ethanol solution is decentralized medium, and the lithium metasilicate, ferrous oxalate, nano silicon and the sucrose that adopt ball grinding method that step 1 is taken by weighing are scattered in the water-ethanol solution, and jitter time is 2h, obtains mixed liquor; Three, adopt spray drying process that mixed liquor is carried out drying, promptly obtain precursor powder; Four, heat treated: at flow velocity is the N of 2000mL/min
2The precursor powder that protection obtains step 3 down carries out heat treated; Be that 5 ℃/min is warming up to 350 ℃ from room temperature at first with heating rate; And at 350 ℃ of following heat treated 2h, continuing then with heating rate is that 5 ℃/min is warming up to 700 ℃, and 700 ℃ of following heat treated 10h; Naturally cool to room temperature then, promptly obtain lithium ion battery with ferrosilicon silicate of lithium/carbon positive electrode.
The nanometer silicon dioxide particle particle diameter is less than 35nm described in this test procedure one.
Ball grinding method concrete operations described in this test procedure two are following: the lithium metasilicate, ferrous oxalate, nano silicon and the sucrose mixing that at first according to ratio of grinding media to material 19: 1 ball milling ball and step 1 are taken by weighing; Add water-ethanol solution then as dispersant; And be ball milling 2h under the 300rpm at rotational speed of ball-mill, promptly obtain mixed liquor after isolating the ball milling ball; The quality of the dispersant of said adding is 6.5: 1 with the ratio of lithium metasilicate, ferrous oxalate, nano silicon and sucrose gross mass that step 1 takes by weighing; The volume ratio of deionized water and ethanol is 1: 1 in the water-ethanol solution described in this test procedure two.
Spray drying process concrete operations described in this test procedure three are following: the water-ethanol mixed solution that at first will in the mixed liquor of step 2 preparation, add as diluent dilutes; Being diluted to total cation concentration is 0.5mol/L, is that 5L/min, inlet temperature are 250 ℃ N in charging rate then
2Carry out spray drying under the protection, the volume ratio of deionized water and ethanol is 1: 1 in the described water-ethanol solution.
Adopting the lithium ion battery of this test preparation to use ferrosilicon silicate of lithium/carbon positive electrode to be assembled into the R2025 button cell for anodal and lithium sheet as negative pole, is 142mAh/g through the specific discharge capacity that detects under the 0.1C multiplying power.
Test four: a kind of lithium ion battery is specifically accomplished with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode according to the following steps:
One, weighing: at first according to Li: the mol ratio of Fe: Si is to take by weighing lithium acetate, ferrous acetate and nano silicon at 2: 1: 1, takes by weighing glucose by 10% of lithium acetate, ferrous oxalate and nano silicon gross mass then; Two, disperse: with water-ethanol solution is decentralized medium, and the lithium acetate, ferrous acetate, nano silicon and the glucose that adopt ball grinding method that step 1 is taken by weighing are scattered in the water-ethanol solution, and jitter time is 2h, obtains mixed liquor; Three, adopt spray drying process that mixed liquor is carried out drying, promptly obtain precursor powder; Four, heat treated: at flow velocity is the N of 2000mL/min
2The precursor powder that protection obtains step 3 down carries out heat treated; Be that 5 ℃/min is warming up to 350 ℃ from room temperature at first with heating rate; And at 350 ℃ of following heat treated 2h, continuing then with heating rate is that 5 ℃/min is warming up to 700 ℃, and 700 ℃ of following heat treated 10h; Naturally cool to room temperature then, promptly obtain lithium ion battery with ferrosilicon silicate of lithium/carbon positive electrode.
The nanometer silicon dioxide particle particle diameter is less than 35nm described in this test procedure one.
Ultra-sonic dispersion method concrete operations described in this test procedure two are following: the lithium acetate that at first step 1 is taken by weighing, ferrous acetate, nano silicon and glucose join in the water-ethanol solution as dispersant; Be the ultrasonic auxiliary ultrasonic dispersion 2h down of 90Hz in frequency then, promptly obtain mixed liquor; The quality of described dispersant is 7.5: 1 with the ratio of lithium acetate, ferrous acetate, nano silicon and glucose gross mass that step 1 takes by weighing; The volume ratio of deionized water and ethanol is 1: 1 in the water-ethanol solution described in this test procedure two.
Spray drying process concrete operations described in this test procedure three are following: the water-ethanol mixed solution that at first will in the mixed liquor of step 2 preparation, add as diluent dilutes; Being diluted to total cation concentration is 0.5mol/L, is that 5L/min, inlet temperature are 250 ℃ N in charging rate then
2Carry out spray drying under the protection, the volume ratio of deionized water and ethanol is 1: 1 in the described water-ethanol solution.
Adopting the lithium ion battery of this test preparation to use ferrosilicon silicate of lithium/carbon positive electrode to be assembled into the R2025 button cell for anodal and lithium sheet as negative pole, is 160mAh/g through the specific discharge capacity that detects under the 0.1C multiplying power.
Test five: a kind of lithium ion battery is specifically accomplished with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode according to the following steps:
One, weighing: at first according to Li: the mol ratio of Fe: Si is to take by weighing lithium hydroxide, ferrous oxalate and nano silicon at 2: 1: 1, takes by weighing starch by 20% of lithium hydroxide, ferrous oxalate and nano silicon gross mass then; Two, disperse: with water-ethanol solution is decentralized medium, and the lithium hydroxide, ferrous oxalate, nano silicon and the starch that adopt ball grinding method that step 1 is taken by weighing are scattered in the water-ethanol solution, and jitter time is 2h, obtains mixed liquor; Three, adopt spray drying process that mixed liquor is carried out drying, promptly obtain precursor powder; Four, heat treated: at flow velocity is the N of 2000mL/min
2The precursor powder that protection obtains step 3 down carries out heat treated; Be that 5 ℃/min is warming up to 350 ℃ from room temperature at first with heating rate; And at 350 ℃ of following heat treated 2h, continuing then with heating rate is that 5 ℃/min is warming up to 700 ℃, and 700 ℃ of following heat treated 10h; Naturally cool to room temperature then, promptly obtain lithium ion battery with ferrosilicon silicate of lithium/carbon positive electrode.
The nanometer silicon dioxide particle particle diameter is less than 35nm described in this test procedure one.
Ball grinding method concrete operations described in this test procedure two are following: the lithium hydroxide, ferrous oxalate, nano silicon and the starch mixing that at first according to ratio of grinding media to material 19: 1 ball milling ball and step 1 are taken by weighing; Add water-ethanol solution then as dispersant; And be ball milling 2h under the 300rpm at rotational speed of ball-mill, promptly obtain mixed liquor after isolating the ball milling ball; The quality of the dispersant of said adding is 6.5: 1 with the ratio of lithium hydroxide, ferrous oxalate, nano silicon and starch gross mass that step 1 takes by weighing; The volume ratio of deionized water and ethanol is 1: 1 in the water-ethanol solution described in this test procedure two.
Spray drying process concrete operations described in this test procedure three are following: the water-ethanol mixed solution that at first will in the mixed liquor of step 2 preparation, add as diluent dilutes; Being diluted to total cation concentration is 0.5mol/L, is that 5L/min, inlet temperature are 250 ℃ N in charging rate then
2Carry out spray drying under the protection, the volume ratio of deionized water and ethanol is 1: 1 in the described water-ethanol solution.
Adopting the lithium ion battery of this test preparation to use ferrosilicon silicate of lithium/carbon positive electrode to be assembled into the R2025 button cell for anodal and lithium sheet as negative pole, is 135mAh/g through the specific discharge capacity that detects under the 0.1C multiplying power.
Claims (10)
1. a lithium ion battery is with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode; It is characterized in that lithium ion battery accomplishes with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode according to the following steps: one, weighing: at first according to Li: the mol ratio of Fe: Si is (1.9～2.1): (0.95～1.05): 1 takes by weighing lithium salt compound, molysite compound and nano silicon, takes by weighing carbon-source cpd by 0.1%～25% of lithium salt compound, molysite compound and nano silicon gross mass then; Two, disperse: with deionized water or water-ethanol solution is decentralized medium; The lithium salt compound, molysite compound, nano silicon and the carbon-source cpd that adopt ball grinding method or ultra-sonic dispersion method that step 1 is taken by weighing are scattered in deionized water or the water-ethanol solution; Jitter time is 0.5h～3h, obtains mixed liquor; Three, adopt spray drying process that mixed liquor is carried out drying, promptly obtain precursor powder; Four, heat treated: at flow velocity is that the precursor powder that under the inert gas shielding of 100mL/min～5000mL/min step 3 is obtained carries out heat treated; Be that 1 ℃/min～20 ℃/min is warming up to 300 ℃～450 ℃ from room temperature at first with heating rate; And at 300 ℃～450 ℃ following heat treated 0.5h～3h; Continuing then with heating rate is that 1 ℃/min～20 ℃/min is warming up to 500 ℃～750 ℃; And 500 ℃～750 ℃ following heat treated 1h～24h, naturally cool to room temperature then, promptly obtain lithium ion battery with ferrosilicon silicate of lithium/carbon positive electrode.
2. a kind of lithium ion battery according to claim 1 is characterized in that with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode lithium salt compound described in the step 1 is selected from lithium metasilicate, lithium metasilicate, lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium chloride, lithium nitrate and lithium phosphate.
3. a kind of lithium ion battery according to claim 2 is characterized in that with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode the compound of molysite described in the step 1 is selected from ferrous oxalate, ferrous acetate, frerrous chloride and ferrous phosphate.
4. a kind of lithium ion battery according to claim 3 is characterized in that with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode the particle diameter of nanometer silicon dioxide particle described in the step 1 is less than 35nm.
5. according to claim 1,2,3 or 4 described a kind of lithium ion batteries preparation method, it is characterized in that carbon-source cpd described in the step 1 is selected from sucrose, glucose, fructose, citric acid, phenolic resins, coal tar asphalt, petroleum asphalt and starch with ferrosilicon silicate of lithium/carbon positive electrode.
6. a kind of lithium ion battery according to claim 5 is with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode; It is characterized in that the ball grinding method concrete operations described in the step 2 are following: at first according to ball material mass ratio (18～20): 1 lithium salt compound, molysite compound, nano silicon and carbon-source cpd mixing that ball milling ball and step 1 are taken by weighing; Add water or water-ethanol solution then as dispersant; And be ball milling 0.5h～3h under 200rpm～400rpm at rotational speed of ball-mill, promptly obtain mixed liquor after isolating the ball milling ball; The quality of the dispersant of said adding is (5～8) with the ratio of lithium salt compound, molysite compound, nano silicon and carbon-source cpd gross mass that step 1 takes by weighing: 1.
7. a kind of lithium ion battery according to claim 5 is with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode; It is characterized in that the ultra-sonic dispersion method concrete operations described in the step 2 are following: the lithium salt compound that at first step 1 is taken by weighing, molysite compound, nano silicon and carbon-source cpd join in the water or water-ethanol solution as dispersant; Be ultrasonic auxiliary ultrasonic dispersion 0.5h～3h down of 80kHz～100kHz in frequency then, promptly obtain mixed liquor; The quality of described dispersant is (5～10) with the ratio of lithium salt compound, molysite compound, nano silicon and carbon-source cpd gross mass that step 1 takes by weighing: 1.
8. a kind of lithium ion battery according to claim 5 is with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode, it is characterized in that the volume ratio of deionized water and ethanol is (0.2～1.8) in the water-ethanol solution described in the step 2: 1.
9. a kind of lithium ion battery according to claim 8 is with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode; It is characterized in that the spray drying process concrete operations described in the step 3 are following: the water or the water-ethanol mixed solution that at first will in the mixed liquor of step 2 preparation, add as diluent dilute; Being diluted to total cation concentration is 0.1mol/L～1mol/L, is that 0.5L/min～10L/min, inlet temperature are 200 ℃～300 ℃ N in charging rate then
2Or carrying out spray drying under the Ar protection, the volume ratio of deionized water and ethanol is (0.2～1.8) in the described water-ethanol solution: 1.
10. a kind of lithium ion battery according to claim 9 is with the preparation method of ferrosilicon silicate of lithium/carbon positive electrode; It is characterized in that the inert gas described in the step 4 is nitrogen, argon gas, hydrogen-nitrogen mixed gas or hydrogen-argon-mixed; The volume content of hydrogen is 0.5%～10% in wherein said hydrogen-nitrogen mixed gas, and the volume content of wherein said hydrogen-argon-mixed middle hydrogen is 0.5%～10%.
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