CN103606672A - Rod-shaped nano iron oxide electrode material, and preparation method and application thereof - Google Patents

Rod-shaped nano iron oxide electrode material, and preparation method and application thereof Download PDF

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CN103606672A
CN103606672A CN201310476413.2A CN201310476413A CN103606672A CN 103606672 A CN103606672 A CN 103606672A CN 201310476413 A CN201310476413 A CN 201310476413A CN 103606672 A CN103606672 A CN 103606672A
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rod
preparation
nano
iron oxide
electrode material
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曾宏
武英
戚雯
况春江
周少雄
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Advanced Technology and Materials Co Ltd
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Advanced Technology and Materials Co Ltd
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Priority to PCT/CN2014/075130 priority patent/WO2015051627A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • H—ELECTRICITY
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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01G49/06—Ferric oxide (Fe2O3)
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a rod-shaped nano iron oxide electrode material, and a preparation method thereof. The preparation method comprises the steps of carrying out a hydrothermal reaction by using FeCl3.6H2O, ammonium dihydrogen phosphate and water as raw materials; and washing produced precipitate to obtain the rod-shaped nano iron oxide. The nano iron oxide is in a rod shape, with an average diameter being 60-80 nm, length being 250-300 nanometers, purity higher than 99.9% and crystal phase being alpha-Fe2O3. The rod-shaped nano iron oxide electrode material can be used as both a positive electrode active material and a negative electrode active material for a lithium ion battery. Raw materials used in the preparation method are easily available, nontoxic and pollution-free to environment. A preparation process is simple; operation is convenient; and the preparation method is suitable for large-scale production. By using the rod-shaped nano iron oxide electrode material as the positive and negative electrode active materials for the lithium ion battery, cost is low; electrochemical performance is excellent; chemical stability of the electrode material is stable; specific capacity is high; and polarization of a charge and discharge platform is small.

Description

Rod-like nano iron oxide electrode material and its preparation method and application
Technical field
The invention belongs to the preparing technical field of lithium ion battery electrode material, be particularly related to a kind of rod-like nano iron oxide electrode material and its preparation method and application, this rod-like nano iron oxide pattern rule, size homogeneous, purity are high, and can be used as positive and negative electrode material.
Background technology
Lithium ion battery as a kind of novel high-energy battery have that energy density is high, the advantage such as long service life, good cycle and memory-less effect, be widely used in mobile electronic product as mobile phone, notebook computer, digital camera etc.In recent years, lithium ion battery should be in fields such as electric automobile, electric tool, intelligent grid, distributed energy resource system, Aero-Space, national defence, and becoming 21 century has one of energy storage device of using value most.
Iron oxide nano material owing to thering is high theoretical specific capacity, enrich reserves, easily preparation, nontoxic, environmental friendliness, cost be low, becomes the study hotspot in lithium ion battery material field.The synthetic method of common nano-sized iron oxide has mechanical ball-milling method, hydro-thermal reaction or take FeOOH nanometer rods has synthesized iron oxide nano material as presoma passes through self-assembly method and the methods such as heat treatment subsequently layer by layer.
Though machinery ball-milling method method is simple there is following defect: the material purity of acquisition is low, contains other impurity, and the material of preparation is generally graininess, and distribution of particles is inhomogeneous.
Existing, pass through in the method for hydro-thermal reaction synthesis of nano iron oxide, generally there is following defect: obtaining of raw material is not easy, such as in the publication number patent application that is CN102674472A, ferric chloride hexahydrate being added in nano-cellulose, this nano-cellulose also needs to use special method to be prepared, so obtaining of raw material is more complicated; In raw material, contain poisonous organic principle, contaminated environment etc.
The FeOOH nanometer rods of take is prepared the method for nano-sized iron oxide as presoma, generally will add alkali, and environment is had to pollution, and in addition, the material of acquisition must be in 600 degree left and right annealing, and technological process is longer, complex operation step, and efficiency is low, and energy consumption is high.
The nano-sized iron oxide of preparing by said method at present is generally used as lithium ion battery negative material, substantially as positive electrode, does not use, and positive electrode is used lithium salts such as LiFePO4 conventionally.The main composition material of lithium ion battery comprises electrolyte, isolated material, positive and negative pole material etc., and positive electrode occupies larger proportion (mass ratio of positive and negative pole material is 3:1～4:1), and its cost directly determines battery cost height.Therefore researching and developing positive electrode is cheaply the demand in market.
Summary of the invention
For the defect existing in prior art, one of object of the present invention is to provide a kind of preparation method of rod-like nano iron oxide electrode material.The method is simple.
Two of object of the present invention is to provide a kind of and adopts rod-like nano iron oxide electrode material prepared by said method and apply in lithium ion battery.The rod-like nano iron oxide obtaining not only has relatively homogeneous of larger specific area, pattern rule, size, and chemical property is good.
To achieve these goals, the present invention is by the following technical solutions:
A preparation method for rod-like nano iron oxide electrode material, with FeCl 36H 2o, ammonium dihydrogen phosphate (NH 4h 2pO 4) and water be that raw material carries out hydro-thermal reaction, the sediment of generation through washing after obtain rod-like nano ferric oxide powder.
The mechanism of above-mentioned hydro-thermal reaction is:
NH 4H 2PO 4=NH 3 ++H 3PO 4 -
H 3PO 4 -+H 2O=H 3PO 4+OH -
FeCl 3·6H 2O=FeCl 3+6H 2O
3OH -+Fe 3+=Fe(OH) 3↓
2Fe(OH) 3=Fe 2O 3↓+3H 2O
In the preparation method of above-mentioned rod-like nano iron oxide electrode material, as a kind of preferred implementation, the temperature of described hydro-thermal reaction is 200-240 ℃, and the time of hydro-thermal reaction is 1-10h.Exemplarily, the temperature of described hydro-thermal reaction is 202 ℃, 210 ℃, 218 ℃, 225 ℃, 230 ℃, 235 ℃ or 238 ℃, and the time of hydro-thermal reaction is 1.5h, 2h, 2.5h, 3h, 4h, 5h, 6h, 7h, 8h, 8.5h or 9.5h.More preferably, the temperature of described hydro-thermal reaction is 210-230 ℃, and the time of hydro-thermal reaction is 4-5h.
In the preparation method of above-mentioned rod-like nano iron oxide electrode material, as a kind of preferred implementation, FeCl in described raw material 36H 2the mol ratio of O and ammonium dihydrogen phosphate is 26:1-30:1, can be exemplarily 26.5:1,27:1,28:1,29:1 or 29.5:1.Preferably, FeCl in described raw material 36H 2the mol ratio of O and ammonium dihydrogen phosphate is 27:1-28:1.
In the preparation method of above-mentioned rod-like nano iron oxide electrode material, as a kind of preferred implementation, described sediment adopts deionized water and alcohol to wash successively.
A rod-like nano iron oxide electrode material of preparing by said method, is bar-shaped, and average diameter is 60-80 nanometer, and length is 250-300 nanometer, and purity is more than 99.9%, and crystalline phase is α-Fe 2o 3.
The application of above-mentioned rod-like nano iron oxide electrode material in lithium ion battery, described rod-like nano iron oxide electrode material is as the active material of the negative or positive electrode of lithium ion battery.Preferably, the concrete grammar of described application is as follows:
Step 1, adds binding agent and conductive agent in above-mentioned rod-like nano ferric oxide powder, by grinding, fully mixes, and then mixing disposed slurry is filtered, to obtain the refining slurries of uniform precoating;
Step 2, coats respectively aluminium foil surface collector and copper foil surface collector by the refining slurries of described precoating, makes anode electrode slice and the battery cathode electrode slice with active material after drying.
In above-mentioned application, as a kind of preferred implementation, in described step 1, the mass percent of described binding agent, conductive agent and rod-like nano croci is: binding agent: 10-20%; Conductive agent: 10-30%; Rod-like nano ferric oxide powder: 50-80%.More preferably, binding agent: 10; Conductive agent: 20%; Rod-like nano croci: 70%.
In above-mentioned application, as a kind of preferred implementation, in described step 1, described milling time is 40-60min, and exemplarily, described milling time is 42min, 45min, 50min, 55min or 58min.
In above-mentioned application, as a kind of preferred implementation, in described step 2, the temperature of described oven dry is 100-120 ℃, and drying time is 18-24h.Exemplarily, described bake out temperature is 105 ℃, 110 ℃, 102 ℃, 108 ℃ or 120 ℃, and drying time is 18.5h, 20h, 21h, 22h, 23h or 23.5h.
In above-mentioned application, described binding agent and conductive agent are this area common agents.Wherein, binding agent can be polytetrafluoroethylene (PTFE), Kynoar (PVDF), sodium carboxymethylcellulose (CMC) or TPO (PP, PE and other copolymer); Conductive agent can be carbon black super P, electrically conductive graphite, Ketjen black, carbon nano-tube or carbon nano-fiber.
Compared with prior art, the present invention has following beneficial effect:
1) preparation method of rod-like nano croci of the present invention, raw material is easy to get, nontoxic; Reactant can have very wide concentration range, is easy to control; In whole reaction, do not adopt noxious substance, reaction does not need to add surfactant, catalyst etc., environmentally safe yet; Product is easy to separation, and impurity seldom, purity is high; Preparation technology is simple, easy to operate, is easy to large-scale industrial production.
2) adopt rod-like nano croci pattern rule, the size that said method obtains to compare homogeneous, be bar-shaped, average diameter is all about 60-80 nanometer left and right, and length is about 250-300 nanometer left and right all, and the purity of material is high.
3) the both positive and negative polarity active material using above-mentioned rod-like nano croci as lithium ion battery, cost is low, chemical property is good, electrode material chemical stability is good, specific capacity is high, the polarization of charge and discharge platform is little.Through evidence, the positive and negative electrode that this ferric oxide nano rod is made, has good charge and discharge cycles, can be used as the electrode material of lithium ion battery; Ferric oxide nano rod negative material discharges and recharges under condition at electric current 100mAh/g, and discharge capacity reaches 1030mAh/g first, and initial charge capacity reaches 723mAh/g; Ferric oxide nano rod positive pole is under electric current 20mAh/g, and discharge capacity reaches 222.4mAh/g first, the 1st charging capacity 175mAh/g.
Accompanying drawing explanation
Fig. 1 is hydrothermal method synthetic iron oxide (Fe 2o 3) shape appearance figure (low power SEM photo) of nanometer rods (be rod-like nano iron oxide, below all referred to as ferric oxide nano rod), the iron oxide (Fe that when being specially hydrothermal temperature and being 220 ℃ prepared by (embodiment 1) 2o 3) electron scanning micrograph (low power SEM photo) of nanometer rods; From above-mentioned picture, can find out, gained nano material size homogeneous, is bar-shaped, and diameter is all about 60-80 nanometer left and right, and length is about 250-300 nanometer left and right all.
Fig. 2 is hydrothermal method synthetic iron oxide (Fe 2o 3) shape appearance figure (high power SEM photo) of nanometer rods, the iron oxide (Fe that when being specially hydrothermal temperature and being 220 ℃ prepared by (embodiment 1) 2o 3) electron scanning micrograph (high power SEM photo) of nanometer rods.From above-mentioned picture, can find out, gained nano material size homogeneous, is bar-shaped, and diameter is in 60-80 nanometer left and right, about the about 250-300 nanometer of length.
Fig. 3 is hydrothermal method synthetic iron oxide (Fe 2o 3) XRD collection of illustrative plates, (embodiment 1) synthetic iron oxide (Fe when being specially hydrothermal temperature and being 220 ℃ 2o 3) XRD detect collection of illustrative plates, from figure, find that the diffraction maximum of the nano material of preparation is Fe 2o 3the XRD of nanometer rods, can confirm that by XRD spectra product is α-Fe 2o 3phase, characteristic peak is obvious.
Fig. 4 is the Raman collection of illustrative plates of ferric oxide nano rod, (embodiment 1) synthetic iron oxide (Fe when being specially hydrothermal temperature and being 220 ℃ 2o 3) Raman collection of illustrative plates, from collection of illustrative plates, find that the diffraction maximum of the nano material of preparation is Fe 2o 3the Raman peak value of nanometer rods.The Raman structural characterization of ferric oxide nano rod is typical iron oxide feature.By Raman spectrogram, can confirm that product is Fe 2o 3.
Fig. 5 is that to take the ferric oxide nano rod of embodiment 1 preparation be the capacity-voltage curve of the button cell of negative material assembling.As we know from the figure, ferric oxide nano rod negative pole under the test condition of 0.1C, in voltage range 0.01-3V, discharge capacity reaches 1030mAh/g first; The 1st time charging capacity reaches 723mAh/g.
Fig. 6 is that to take the ferric oxide nano rod of embodiment 1 preparation be capacity-cycle-index, coulomb efficiency curve of the button cell of negative material assembling.As we know from the figure, except first to the coulombic efficiency of the 18th time, the coulombic efficiency of other circulations approaches 100%.
Fig. 7 is that to take the ferric oxide nano rod of embodiment 1 preparation be the capacity-voltage curve of positive electrode assembling button cell.As we know from the figure, under the test condition of 0.1C, ferric oxide nano rod is anodal, and in voltage range 1.5-4.5V, discharge capacity reaches 222.4mAh/g first, the 1st charging capacity 175mAh/g, the 2nd discharge capacity 144.4mAh/g.
Fig. 8 is that to take the ferric oxide nano rod of embodiment 1 preparation be capacity (the coulombic efficiency)-cyclic curve of positive electrode assembling button cell.As we know from the figure, except first to the coulombic efficiency of the 10th time, the coulombic efficiency under other cycle-indexes approaches 100%.
Embodiment
Below by embodiment, the present invention is described in detail, but the present invention is not limited to this.
Embodiment 1
The preparation of rod-like nano ferric oxide powder:
Take ferric chloride (FeCl36H2O) (FeCl 36H 2o) 0.972g, ammonium dihydrogen phosphate (NH 4h 2pO 4) 0.01485g(ferric chloride (FeCl36H2O) and ammonium dihydrogen phosphate molar ratio be 26:1) and deionized water 160g, it is all put into hydrothermal reaction kettle, under 220 ℃ of conditions, hydro-thermal reaction time 2h, then naturally cools to room temperature.Again sediment is washed to 3 times, alcohol washing 2 times by deionized water successively, obtain rod-like nano ferric oxide powder after separated, it is 99.9% that HPLC detects purity.
From Fig. 1 and Fig. 2, can find out, gained nano material size homogeneous, is bar-shaped, and average diameter is all about 60-80 nanometer left and right, and length is about 250-300 nanometer left and right all.From Fig. 3 and Fig. 4, can confirm that product is α-Fe 2o 3phase, characteristic peak is obvious.
There is the preparation of anode and the negative electricity pole piece of above-mentioned electrode active material:
According to the mass ratio of 7:1:2, rod-like nano ferric oxide powder, polyfluortetraethylene of binding element (PTFE) and the conductive agent carbon black Super P of preparation are evenly mixed, grind 45 minutes, then filter, obtain the refining slurries of uniform precoating; These slurries are directly coated to aluminium foil surface collector, and the temperature with 110 ℃ is incubated 24h in vacuum drying oven, obtains electrode active material anode electrode slice.These slurries are directly coated to copper foil surface collector, and the temperature with 110 ℃ is incubated 24h in vacuum drying oven, obtains electrode active material battery cathode electrode slice.
Negative electricity pole piece, the lithium sheet prepared by this embodiment of take is positive plate, PE(polyethylene) be barrier film, LiPF 61mol/l DMC:EC:EMC=1:1:1 is that electrolyte is assembled into button cell 1-A.Battery is carried out to constant current charge-discharge experiment, and electric performance test result is referring to Fig. 5 and Fig. 6, and in voltage range 0.01-3V, under 100mA/g current density, discharge capacity reaches 1030mAh/g first; The 1st time charging capacity reaches 723mAh/g, after charge and discharge cycles 100 times, still can maintain 90mAh/g, and except first to the coulombic efficiency of the 18th time, the coulombic efficiency of other circulations approaches 100%.
Anode electrode sheet, the lithium sheet prepared by this embodiment of take is negative plate, PE(polyethylene) be barrier film, LiPF 61mol/l DMC:EC:EMC=1:1:1 is that electrolyte is assembled into button cell 1-B.Battery is carried out to constant current charge-discharge experiment, electric performance test result is referring to Fig. 7 and Fig. 8, in voltage range 1.5-4.5V, under 100mA/g current density, discharge capacity reaches 222.4mAh/g first, the 1st charging capacity 175mAh/g, the 2nd discharge capacity 144.4mAh/g, still can maintain 110mAh/g after charge and discharge cycles 20 times, except first to the coulombic efficiency of the 10th time, the coulombic efficiency under other cycle-indexes approaches 100%.
Embodiment 2
The preparation of rod-like nano ferric oxide powder:
Take ferric chloride (FeCl36H2O) (FeCl 36H 2o) 0.695g, ammonium dihydrogen phosphate (NH 4h 2pO 4) 0.01g(ferric chloride (FeCl36H2O) and ammonium dihydrogen phosphate molar ratio be 30:1) and deionized water 120g, it is all put into hydrothermal reaction kettle, under 220 ℃ of conditions, hydro-thermal reaction time 2h, then naturally cools to room temperature.Again sediment is washed to 3 times, alcohol washing 2 times by deionized water successively, obtain rod-like nano ferric oxide powder after separated, it is 99.9% that HPLC detects purity.
Through low power sem analysis, gained nano material size homogeneous, is bar-shaped, and diameter is all about 60-80 nanometer left and right, and length is about 250-300 nanometer left and right all.Through XRD analysis, can confirm that product is α-Fe 2o 3phase, can be observed obvious α-Fe in 33 ゜, 35.7 ゜, 53.9 ゜ positions 2o 3characteristic peak.
There is the preparation of anode and the negative electricity pole piece of above-mentioned electrode active material: with embodiment 1.
Negative electricity pole piece, the lithium sheet prepared by this embodiment of take is positive plate, PE(polyethylene) be barrier film, LiPF 61mol/l DMC:EC:EMC=1:1:1 is that electrolyte is assembled into button cell 2-A.Battery is carried out to constant current charge-discharge experiment, and in voltage range 0.01-3V, under 100mA/g current density, discharge capacity reaches 1384mAh/g first; The 1st time charging capacity reaches 773mAh/g, after charge and discharge cycles 100 times, still can maintain 200mAh/g, and except first to the coulombic efficiency of the 3rd time, the coulombic efficiency of other circulations approaches 100%.
Anode electrode sheet, the lithium sheet prepared by this embodiment of take is negative plate, PE(polyethylene) be barrier film, LiPF 61mol/l DMC:EC:EMC=1:1:1 is that electrolyte is assembled into button cell 2-B.Battery is carried out to constant current charge-discharge experiment, in voltage range 1.5-4.5V, under 100mA/g current density, discharge capacity reaches 197mAh/g first, the 1st charging capacity 169mAh/g, after charge and discharge cycles 20 times, still can maintain 98mAh/g, except first to the coulombic efficiency of the 2nd time, the coulombic efficiency under other cycle-indexes approaches 100%.
Embodiment 3
The preparation of rod-like nano ferric oxide powder: except hydrothermal reaction condition is that 205 ℃, reaction time are 8h, other are all identical with the preparation method of the rod-like nano ferric oxide powder of embodiment 1.
Through low power sem analysis, gained nano material size homogeneous, is bar-shaped, and diameter is all about 60-80 nanometer left and right, and length is about 250-300 nanometer left and right all.Through XRD analysis, can confirm that product is α-Fe 2o 3phase, can be observed obvious α-Fe in 33.1 ゜, 35.6 ゜, 53.8 ゜ positions 2o 3characteristic peak.
There is the preparation of anode and the negative electricity pole piece of above-mentioned electrode active material: with embodiment 1.
Negative electricity pole piece, the lithium sheet prepared by this embodiment of take is positive plate, PE(polyethylene) be barrier film, LiPF 61mol/l DMC:EC:EMC=1:1:1 is that electrolyte is assembled into button cell 3-A.Battery is carried out to constant current charge-discharge experiment, and in voltage range 0.01-3V, under 100mA/g current density, discharge capacity reaches 1281mAh/g first; The 1st time charging capacity reaches 781mAh/g, after charge and discharge cycles 50 times, still can maintain 330mAh/g, and except first to the coulombic efficiency of the 2nd time, the coulombic efficiency of other circulations approaches 100%.
Anode electrode sheet, the lithium sheet prepared by this embodiment of take is negative plate, PE(polyethylene) be barrier film, LiPF 61mol/l DMC:EC:EMC=1:1:1 is that electrolyte is assembled into button cell 3-B.Battery is carried out to constant current charge-discharge experiment, in voltage range 1.5-4.5V, under 100mA/g current density, discharge capacity reaches 183mAh/g first, the 1st charging capacity 174mAh/g, after charge and discharge cycles 20 times, still can maintain 83mAh/g, except first to the coulombic efficiency of the 2nd time, the coulombic efficiency under other cycle-indexes approaches 100%.
Embodiment 4
The preparation of rod-like nano ferric oxide powder: except hydrothermal reaction condition is that 240 ℃, reaction time are 4h, other are all identical with the preparation method of the rod-like nano ferric oxide powder of embodiment 1.
Through low power sem analysis, gained nano material size homogeneous, is bar-shaped, and diameter is all about 60-80 nanometer left and right, and length is about 250-300 nanometer left and right all.Through XRD analysis, can confirm that product is α-Fe 2o 3phase, can be observed obvious α-Fe in 33 ゜, 35.7 ゜, 53.9 ゜ positions 2o 3characteristic peak.
There is the preparation of anode and the negative electricity pole piece of above-mentioned electrode active material: with embodiment 1.
Negative electricity pole piece, the lithium sheet prepared by this embodiment of take is positive plate, PE(polyethylene) be barrier film, LiPF 61mol/l DMC:EC:EMC=1:1:1 is that electrolyte is assembled into button cell 4-A.Battery is carried out to constant current charge-discharge experiment, in voltage range 0.01-3V, under 100mA/g current density, discharge capacity reaches 1083mAh/g first, the 1st time charging capacity reaches 730mAh/g, after charge and discharge cycles 50 times, still can maintain 260mAh/g, except first to the coulombic efficiency of the 2nd time, the coulombic efficiency of other circulations approaches 100%.
Anode electrode sheet, the lithium sheet prepared by this embodiment of take is negative plate, PE(polyethylene) be barrier film, LiPF 61mol/l DMC:EC:EMC=1:1:1 is that electrolyte is assembled into button cell 4-B.Battery is carried out to constant current charge-discharge experiment, in voltage range 1.5-4.5V, under 100mA/g current density, discharge capacity reaches 206mAh/g first, the 1st charging capacity 181mAh/g, after charge and discharge cycles 20 times, still can maintain 106mAh/g, except first to the coulombic efficiency of the 2nd time, the coulombic efficiency under other cycle-indexes approaches 100%.
The purposes that should be appreciated that these embodiment only limits the scope of the invention for the present invention being described but not being intended to.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various changes, modification and/or modification to the present invention, within these all equivalent form of values fall within the protection range that the application's appended claims limits equally.

Claims (10)

1. a preparation method for rod-like nano iron oxide electrode material, is characterized in that, with FeCl 36H 2o, ammonium dihydrogen phosphate and water are that raw material carries out hydro-thermal reaction, and the sediment of generation obtains rod-like nano ferric oxide powder after washing.
2. preparation method according to claim 1, is characterized in that, the temperature of described hydro-thermal reaction is 200-240 ℃, and the time of hydro-thermal reaction is 1-10h.Preferably, the temperature of described hydro-thermal reaction is 210-230 ℃, and the time of hydro-thermal reaction is 5-6h.
3. preparation method according to claim 1, is characterized in that, FeCl in described raw material 36H 2the mol ratio of O and ammonium dihydrogen phosphate is 26:1-30:1,
4. preparation method according to claim 3, is characterized in that, FeCl in described raw material 36H 2the mol ratio of O and ammonium dihydrogen phosphate is 27:1-28:1.
5. preparation method according to claim 1, is characterized in that, described sediment adopts deionized water and alcohol to wash successively.
6. a rod-like nano iron oxide electrode material of preparing by the arbitrary described method of claim 1-5, is characterized in that, is bar-shaped, and average diameter is 60-80 nanometer, and length is 250-300 nanometer, and purity is more than 99.9%, and crystalline phase is α-Fe 2o 3.
7. the application of rod-like nano iron oxide electrode material in lithium ion battery described in claim 6, is characterized in that, described rod-like nano iron oxide electrode material is as the positive pole of lithium ion battery and the active material of negative pole.
8. application according to claim 7, is characterized in that, concrete application process is as follows:
Step 1, adds binding agent and conductive agent in above-mentioned rod-like nano ferric oxide powder, by grinding, fully mixes, and then mixing disposed slurry is filtered, to obtain the refining slurries of uniform precoating;
Step 2, coats respectively aluminium foil surface collector and copper foil surface collector by the refining slurries of described precoating, makes anode electrode slice and the battery cathode electrode slice with active material after drying.
9. application according to claim 8, is characterized in that, in described step 1, the mass percent of described binding agent, conductive agent and rod-like nano croci is: binding agent: 10-20%; Conductive agent: 10-30%; Rod-like nano ferric oxide powder: 50-80%.Preferably, binding agent: 10%; Conductive agent: 20%; Rod-like nano croci: 70%.
10. application according to claim 8, is characterized in that, in described step 1, described milling time is 40-60min; In described step 2, the temperature of described oven dry is 100-120 ℃, and drying time is 18-24h.
CN201310476413.2A 2013-10-12 2013-10-12 Rod-shaped nano iron oxide electrode material, and preparation method and application thereof Pending CN103606672A (en)

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WO2015051627A1 (en) * 2013-10-12 2015-04-16 安泰科技股份有限公司 Rod-shaped nano iron oxide electrode material, and preparation method therefor and application thereof
CN104815658A (en) * 2015-04-09 2015-08-05 太原理工大学 Tetrahexahedron iron oxide nanocrystalline catalyst, preparation method and application thereof
CN104815658B (en) * 2015-04-09 2017-04-12 太原理工大学 Tetrahexahedron iron oxide nanocrystalline catalyst, preparation method and application thereof
WO2018184183A1 (en) * 2017-04-07 2018-10-11 深圳市佩成科技有限责任公司 Method of manufacturing lithium-ion battery electrode and assembling battery
CN106972152A (en) * 2017-04-07 2017-07-21 深圳市佩成科技有限责任公司 Lithium ion cell electrode preparation and the assemble method of battery
CN107313065A (en) * 2017-07-14 2017-11-03 西南大学 Iron phosphide modified alpha type iron oxide vermiform nano-structure array light anode and its preparation method and application
CN107313065B (en) * 2017-07-14 2019-01-04 西南大学 Iron phosphide modified alpha type iron oxide vermiform nano-structure array light anode and its preparation method and application
CN108390046A (en) * 2018-03-16 2018-08-10 福州大学 A kind of preparation method of rodlike α-di-iron trioxide/GN lithium cell negative pole materials
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CN108383167A (en) * 2018-04-18 2018-08-10 中国科学院青海盐湖研究所 A kind of preparation method of rodlike alpha-type ferric oxide
CN112951619A (en) * 2021-01-29 2021-06-11 多助科技(武汉)有限公司 Iron oxide @ manganese dioxide core-shell structure material and preparation and application thereof
CN113184914A (en) * 2021-04-20 2021-07-30 广东工业大学 Porous capsule-shaped Fe2O3Nano material and preparation method and application thereof
CN114394626A (en) * 2022-01-20 2022-04-26 西南石油大学 Preparation method of rod-like ferric oxide negative electrode material of lithium ion battery

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