CN103956463A - Preparation method of lithium iron phosphate-manganese oxide binary lithium battery cathode material - Google Patents

Preparation method of lithium iron phosphate-manganese oxide binary lithium battery cathode material Download PDF

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CN103956463A
CN103956463A CN201410173222.3A CN201410173222A CN103956463A CN 103956463 A CN103956463 A CN 103956463A CN 201410173222 A CN201410173222 A CN 201410173222A CN 103956463 A CN103956463 A CN 103956463A
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lithium
manganese oxide
lifepo4
iron phosphate
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CN103956463B (en
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陈庆
曾军堂
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Jiangxi Beston Electronics Technology Co Ltd
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Chengdu New Keli Chemical Science Co Ltd
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method of a lithium iron phosphate-manganese oxide binary lithium battery cathode material. The method comprises the following steps of inlaying through grains of lithium iron phosphate and manganese oxide lithium under the action of a crystalline phase growing inductive agent and the powerful shearing section action of a length-diameter ratio twin-screw extruder, and arranging ions by virtue of a strong electric field and crystallizing so as to form the binary lithium battery cathode material comprising alternating piece-shaped lithium iron phosphate and layer-shaped manganese oxide lithium. The method provided by the invention has the advantages that inherent disadvantages of respective crystal structures of piece-shaped lithium iron phosphate and layer-shaped manganese oxide lithium generated when direct mixing coating and core-shell structure coating are adopted are overcome, the disadvantage of single coating in the prior art that the properties of piece-shaped lithium iron phosphate and layer-shaped manganese oxide lithium cannot fully complement each other is solved, the obtained lithium iron phosphate-manganese oxide binary lithium battery cathode material has the characteristics of high conductivity, good stability at high and low temperatures, good cycle structure stability, high density and high electric capacity, and the method can be put into industrial production favorably.

Description

A kind of preparation method of LiFePO4-manganese oxide lithium binary anode material of lithium battery
Technical field
The present invention relates to battery material field, be specifically related to a kind of preparation method of LiFePO4-manganese oxide lithium binary anode material of lithium battery.
Background technology
At present, electric automobile has become one of effective means of alleviating consumption of petroleum and solution environmental pollution.The core of development electric motor car is safety, efficient secondary battery.At present, main plumbic acid and the Ni-MH battery of using in electric motor car or hybrid electric vehicle, because useful life is short, easily contaminated environment, is progressively replaced by lithium ion battery safely and efficiently.Lithium ion battery is a kind of novel secondary energy-storage battery growing up the nineties in 20th century.Owing to thering is high-energy, long-life, low consumption, nuisanceless, memory-less effect and the advantage such as self discharge is little, internal resistance is little, cost performance is high, pollution is few, be widely used in the fields such as mobile phone, notebook computer, video camera, digital camera, electric automobile.
In lithium ion battery industrialization promotion, to having relatively high expectations of battery capacity, fail safe, integrated cost, positive electrode becomes Main Bottleneck.At present, anode material for lithium-ion batteries mainly contains cobalt acid lithium, lithium nickelate, LiMn2O4 and LiFePO4 etc., wherein due to cobalt and nickel resources limited, can only be used for small-sized lithium electricity positive electrode; And LiFePO4 (LiFePO 4), LiMn2O4 (LiMn 2o 4), stratiform manganese oxide lithium (LiMnO2) has wide material sources, low price, Heat stability is good, no hygroscopicity, environmentally friendly, is applicable to large-scale development and uses, and is more suitable for the electric automobile in large capacity requirement.
LiFePO4 (the LiFePO of olivine-type structure 4) there is reversible removal lithium embedded characteristic within 1997, being in the news since, so that its security performance is good, cycle performance is excellent, abundant, the low cost and other advantages of environmental friendliness, raw material sources and become the main positive electrode of lithium ion battery.But, LiFePO4 (LiFePO 4) as anode material of lithium battery, still there is defect, also electric energy relatively low, that low-temperature stability is poor, tap density is little, unit volume battery is stored is less to be mainly manifested in poor, the chargeable voltage of electronic conductivity of LiFePO4, Fe in preparation 2+oxidizable one-tenth Fe 3+, be difficult to obtain single-phase LiFePO 4, purity is low, and complicated process of preparation needs long-time high-temperature calcination, and energy consumption is high, the cycle is long.Although the doping by lithium position, iron position improves ion and electronic conductivity, by improving particle diameter and the pattern control effecting reaction area of particle, by adding extra conductive agent to increase electron conduction etc. to improve the cryogenic property of LiFePO4, but the inherent characteristics of LiFePO 4 material, determines that its cryogenic property is inferior to other positive electrodes such as LiMn2O4.
Manganese oxide lithium (the LiMnO of layer structure 2) there is the theoretical capacity up to 286mAh/g, superior electrical property, but because the backward spinel structure of de-lithium changes, the variation repeatedly of crystalline structure very easily causes volumetric expansion and contraction, stable circulation performance is bad, and especially high temperature cyclic performance is poor, easily solution loss.
In order to make up the defect of LiFePO4 and stratiform manganese oxide lithium, technical staff attempts to carry out improvement in performance by the two compound means.As:
Chinese invention patent CN103531801 A discloses a kind of modified phosphate iron lithium anode material, formed by grinding and sintering by LiFePO4 500 powder, manganese dioxide 4-5 part, stratiform nickle cobalt lithium manganate 4-5 part, expanded perlite 3-4 part, modification silver powder 4-5 part, this invention has improved material conductivity by manganese dioxide and stratiform nickle cobalt lithium manganate, and effectively suppress growing up of crystal, obtain homodisperse LiFePO 4 material.But this invention is carried out surface modification in type LiFePO4, its modification rests on large particle surface, and in charge and discharge process, particle volume fluctuating stress is inconsistent, and cyclical stability is poor, and especially the cryogenic property of LiFePO4 cannot be changed.
Chinese invention patent CN101916848A discloses a kind of LiFePO 4 coating LiMn 2 O 4 composite electrode material and preparation method thereof, and this technology is with LiMn 2o 4for matrix, at its surperficial clad nano level LiFePO 4, make the LiMn of internal layer 2o 4electrode material and electrolyte separate, and can suppress reacting of electrode and electrolyte, reduce the molten damage of manganese.Although this invention is coated on LiFePO4 with nano shape the surface of LiMn2O4, overcome the defect of the poor and molten damage of LiMn2O4 stable circulation, the electrical conductance of combination electrode material and high temperature resistant, resistance to low temperature do not get a promotion.
Chinese invention patent CN 101740752A discloses a kind of composite anode material for lithium ion battery with nucleocapsid structure, this composite positive pole stratum nucleare active material is the one in LiFePO4, LiMn2O4, shell active material is the LiFePO4 that is compounded with carbon, by shell-nuclear compounded structure, there is excellent chemical property, excellent cycle performance, can adapt to working at ultra-low temperature environment.But this invention, owing to being that a kind of simple particle is coated, is therefore failed the advantage complete complementary of LiFePO4, LiMn2O4, and its high temperature stability performance fails to be changed.
According to above-mentioned, security performance is good owing to having for LiFePO4 and manganese oxide lithium, nontoxic pollution-free, low cost and other advantages, be considered to the most promising anode material for lithium-ion batteries, but have defect separately, LiFePO4 electrical conductance is poor, low-temperature stability is poor, capacitance is lower, density is low; Stratiform manganese oxide lithium cyclical stability is poor, poor high temperature stability.According to prior art, the compound of LiFePO4 and manganese oxide lithium can carry out performance complement, but rest on the coated and core-shell structure of particle surface due to compound, therefore cannot obtain the composite positive pole that electric conductivity, resistance to low temperature, resistance to elevated temperatures, stable circulation performance have concurrently simultaneously.
Summary of the invention
There is as anode material for lithium-ion batteries the defect that conductivity is low, low-temperature stability is poor, capacitance is low for existing olivine-type LiFePO4, and stratiform manganese oxide lithium structure cyclical stability is poor, the defect of poor high temperature stability, the invention provides a kind of preparation method of LiFePO4-manganese oxide lithium binary anode material of lithium battery.This preparation method induces, shears section by crystalline phase, makes LiFePO4 form laminated structure by dynamic response, by the regular ion of highfield form a kind of layer alternate be LiFePO4-manganese oxide lithium binary anode material of lithium battery that crystal grain is inlayed.The intrinsic defect of crystalline structure separately when the method has overcome the coated and core-shell structure of direct blend, the LiFePO4-manganese oxide lithium binary positive electrode obtaining has high, the high low-temperature stabilization of conductivity, loop structure good stability, density is high, capacitance is high feature.Not only mutually make up the defect that LiFePO4 capacity is low, density is low, low-temperature stability is poor, and the Stability Analysis of Structures of stratiform manganese oxide lithium, heat-resisting quantity are promoted, the advantage of the two is fully brought into play.
Concrete summary of the invention is as follows:
The preparation method of a kind of LiFePO4-manganese oxide of the present invention lithium binary anode material of lithium battery, it is characterized in that: this LiFePO4-manganese oxide lithium binary anode material of lithium battery be a kind of layer alternate be the composite material that crystal grain is inlayed, wherein can to select conventional lithium source, source of iron, phosphorus source to carry out according to certain mol ratio premixed for LiFePO4, and manganese oxide lithium can select conventional manganese source, lithium source premixed according to certain mol ratio.
A preparation method for LiFePO4-manganese oxide lithium binary anode material of lithium battery, comprises following concrete steps:
1) by the Li:Fe:P=1:1.2-1.3:1 mixing in molar ratio of lithium source, source of iron, phosphorus source, composition LiFePO4 initial feed; Described lithium source is at least one in phosphoric acid hydrogen two lithiums, lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate; Described source of iron is at least one in ferric phosphate, iron oxide, iron chloride, ferric nitrate; Described phosphorus source is at least one in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid; Calculate according to theoretical value, get the LiFePO4 of 40-45% by weight percentage, the three oblique crystal C uSO4 of 0.2-1% are as the agent of crystalline phase growth inducing, and the sodium thiosulfate of 0.5-1%, as reducing agent, disperses 3-5min for subsequent use with the speed high-speed stirred of 1400-5000rpm in high-speed mixer;
2) mixture obtaining in step 1) is pumped into screw extruder, it is that 60 ° of screwing elements, two groups of oblique angles are the screwing element of 90 °, the screwing element of a group reverse-45 ° that screw rod arranges two groups of oblique angles, under crystalline phase growth inducing agent effect, the shearing section of the screwing element utilizing forms flaky lithium iron phosphate in dynamic response;
3) at screw extruder stage casing, back segment, the flaky lithium iron phosphate forming is not also completed into while stablizing crystal grain, pass into manganese dioxide, mangano-manganic oxide, lithium carbonate manganese dioxide in molar ratio: mangano-manganic oxide: the pre-composition of press=1:0.2-0.5:1 of lithium carbonate, calculate according to theoretical value, intake is the stratiform manganese oxide lithium of 54-59% by weight percentage, section is not induced and sheared to LiFePO4, manganese oxide lithium by crystalline phase when complete crystallization, crystal grain is progressively inlayed, and forms by the flaky lithium iron phosphate binary cell positive material alternate with stratiform manganese oxide lithium;
4) at screw extruder end, electric field polarization is set, flaky lithium iron phosphate binary cell positive material under highfield the ion regular arrangement alternate with stratiform manganese oxide lithium that step 3) is obtained, and rapid crystallization, obtain tiny, the uniform LiFePO4-manganese oxide of crystal grain lithium binary anode material of lithium battery.
In above-mentioned preparation method, preparation process 2) described screw extruder is parallel dual-screw extruder, it is characterized in that being provided with shearing screwing element, screwing element oblique angle is the combination of 30 °, 45 °, 60 °, 90 ° ,-45 °, be wherein the reaction of guaranteeing invention shearing section and crystalline phase induction, it is that 60 ° of screwing elements, two groups of oblique angles are that the screwing element of 90 °, the screwing element of a group reverse-45 ° are necessary conditions of the present invention that two groups of oblique angles are set.
In above-mentioned preparation method, preparation process 2) described screw extruder, adopt screw slenderness ratio to be greater than 65/1.
In above-mentioned preparation method, preparation process 2), 3), 4) described in screw extruder, adopt confined reaction, the control temperature of its front end, stage casing, back segment, end is: front end 80-100 DEG C, stage casing 150-200 DEG C, back segment 200-240 DEG C, end 250-300 DEG C, screw speed is controlled at 50-120rpm.
In above-mentioned preparation method, preparation process 4) described in electric field be 100-200KV/m, be arranged on screw extruder end, LiFePO4-manganese oxide lithium binary cell positive material consecutive hours cation Regularization under polarization, and rapid crystallization.
The outstanding feature of the present invention is not induce and shear section by crystalline phase when complete crystallization at LiFePO4, manganese oxide lithium, form the complex between lamellar phase, make the regular and rapid crystallization of ion by highfield, crystal grain is progressively inlayed, thereby obtains LiFePO4-manganese oxide lithium binary material of rock-steady structure.Layer alternate and in meta structure, stratiform manganese oxide lithium (LiMnO2) thus in charge and discharge process, the defect of structural instability is inlayed and is made up by interlayer and LiFePO4 crystal grain, and kept the performance that stratiform manganese oxide lithium (LiMnO2) specific energy is high, conductivity is high.And the chip architecture that LiFePO4 forms by section improves by inlaying electrical conductance with stratiform manganese oxide lithium, low-temperature stability is obviously improved, and especially its tap density is by existing 1.0-1.2 cm 3bring up to 2.2 cm 3above.
The preparation method of a kind of LiFePO4-manganese oxide of the present invention lithium binary anode material of lithium battery, utilize the strong shear section effect of the agent of crystalline phase growth inducing and big L/D ratio screw extruder, make LiFePO4 form laminated structure by dynamic response, and at the stage casing of screw rod and back segment by adding manganese dioxide, mangano-manganic oxide, the pre-composition of lithium carbonate, the crystal grain of LiFePO4 and manganese oxide lithium is inlayed, form by the flaky lithium iron phosphate binary lithium battery battery positive electrode alternate with stratiform manganese oxide lithium, the intrinsic defect of crystalline structure separately when the method has overcome the coated and core-shell structure of direct blend, realize continuous high-efficient and prepared LiFePO4-manganese oxide lithium binary anode material of lithium battery, solve the defect that current single the two performance of coated existence cannot complete complementary, it is high that the LiFePO4-manganese oxide lithium binary positive electrode obtaining has conductivity, high low-temperature stabilization, loop structure good stability, density is high, the feature that capacitance is high.The method not only preparation technology is easily controlled, and reaction evenly, and the construction of stable between lamellar phase is reliable, has not only made up the two defect of LiFePO4 and manganese oxide lithium, and the advantage of the two is fully brought into play.
After testing, the conductivity of LiFePO4-manganese oxide lithium binary anode material of lithium battery exceedes 10 -6s/cm, in the time of-30 DEG C of low temperature, the specific capacity of battery can reach 242mAh/g, and when 80 DEG C of high temperature, the specific capacity of battery exceedes 256mAh/g, high and low temperature resistance excellence, and there is 3.5V stabilised platform voltage; Under 1C discharge-rate, through 100 charging cycle, possess the more than 98% of initial capacity, exceeding in 10C multiplying power discharging situation, without the difference such as blast, distortion, Stability Analysis of Structures, good cycling stability; Apparent density is greater than 1.2g/cm 3, tap density is greater than 2.2g/cm 3.
The preparation method of a kind of LiFePO4-manganese oxide of the present invention lithium binary anode material of lithium battery, compared with existing LiFePO4, LiMn2O4 anode material of lithium battery technology, its outstanding feature is:
1, a kind of preparation method of LiFePO4-manganese oxide lithium binary anode material of lithium battery, utilize the shearing section effect of the agent of crystalline phase growth inducing and big L/D ratio screw extruder, make LiFePO4 form laminated structure by dynamic response, crystal grain forms by the stratiform manganese oxide lithium binary cell positive material alternate with flaky lithium iron phosphate by inlaying.
2, a kind of preparation method of LiFePO4-manganese oxide lithium binary anode material of lithium battery, realize continuous high-efficient and prepared LiFePO4-manganese oxide lithium binary anode material of lithium battery, the intrinsic defect of crystalline structure separately when logical the method has overcome the coated and core-shell structure of direct blend, not only make up the two defect of LiFePO4 and manganese oxide lithium, and the advantage of the two is fully brought into play, the LiFePO4-manganese oxide lithium binary positive electrode obtaining has high, the high low-temperature stabilization of conductivity, loop structure good stability, density is high, capacitance is high feature.
3, the preparation method of a kind of LiFePO4-manganese oxide of the present invention lithium binary anode material of lithium battery, production efficiency is high, equipment investment is low, can continuous operation, low, the without sewage discharge of easy to implement and control, energy consumption, be beneficial to suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the process flow diagram that the preparation method of a kind of LiFePO4-manganese oxide of the present invention lithium binary anode material of lithium battery adopts.
Fig. 2 is the preparation simplified schematic diagram (the brilliant material of flaky lithium iron phosphate and stratiform manganese oxide lithium mosaic map mosaic) of a kind of LiFePO4-manganese oxide of the present invention lithium binary anode material of lithium battery.
Embodiment
Following embodiment, is described in further detail foregoing of the present invention again.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following example.Without departing from the idea case in the present invention described above, various replacements or the change made according to ordinary skill knowledge and customary means, all should comprise within the scope of the invention.
embodiment 1
1) in high-speed mixer by lithium source, source of iron, phosphorus source in molar ratio Li:Fe:P=1:1.2:1 mix, lithium source is phosphoric acid hydrogen two lithiums, source of iron is ferric phosphate, phosphorus source is ammonium dihydrogen phosphate, calculate according to theoretical value, get 45% LiFePO4 by weight percentage, 0.2% three oblique crystal C uSO4 are as the agent of crystalline phase growth inducing, 0.5% sodium thiosulfate, as reducing agent, disperses 3min for subsequent use with the speed high-speed stirred of 2000rpm;
2) mixture obtaining in step 1) is pumped into screw extruder, it is that 60 ° of screwing elements, two groups of oblique angles are the screwing element of 90 ° that screw rod arranges two groups of oblique angles, the screwing element of one group reverse-45 °, under crystalline phase growth inducing agent effect, the shearing section of the screwing element utilizing forms flaky lithium iron phosphate in dynamic response;
3) at screw extruder stage casing, back segment, the flaky lithium iron phosphate forming is not also completed into while stablizing crystal grain, pass into manganese dioxide, mangano-manganic oxide, lithium carbonate manganese dioxide in molar ratio: mangano-manganic oxide: the pre-composition of press=1:0.2:1 of lithium carbonate, calculate according to theoretical value, intake is 54.3% stratiform manganese oxide lithium by weight percentage, the crystal grain of LiFePO4 and manganese oxide lithium is inlayed, and forms by the flaky lithium iron phosphate binary cell positive material alternate with stratiform manganese oxide lithium;
4) at screw extruder end, electric field is set, flaky lithium iron phosphate binary cell positive material under highfield the ion regular arrangement alternate with stratiform manganese oxide lithium that step 3) is obtained, and rapid crystallization, obtain tiny, the uniform LiFePO4-manganese oxide of crystal grain lithium binary anode material of lithium battery.
After testing, LiFePO4-manganese oxide lithium binary anode material of lithium battery is in the time of-30 DEG C of low temperature, and the specific capacity of battery can reach 244mAh/g, the specific capacity 258mAh/g of battery when 80 DEG C of high temperature; Under 1C discharge-rate, through 100 charging cycle, specific capacity 255mAh/g, Stability Analysis of Structures, good cycling stability; Tap density 2.25g/cm 3.
embodiment 2
1) in high-speed mixer by lithium source, source of iron, phosphorus source in molar ratio Li:Fe:P=1:1.3:1 mix, lithium source is lithium carbonate, source of iron is iron oxide, phosphorus source is ammonium dihydrogen phosphate, calculate according to theoretical value, get 43 LiFePO4 by weight percentage, 0.5% three oblique crystal C uSO4 are as the agent of crystalline phase growth inducing, 0.8% sodium thiosulfate, as reducing agent, disperses 5min for subsequent use with the speed high-speed stirred of 3000rpm;
2) mixture obtaining in step 1) is pumped into screw extruder, it is that 60 ° of screwing elements, two groups of oblique angles are the screwing element of 90 ° that screw rod arranges two groups of oblique angles, the screwing element of one group reverse-45 °, the screwing element of a group 30 °, under crystalline phase growth inducing agent effect, the shearing section of the screwing element utilizing forms flaky lithium iron phosphate in dynamic response;
3) at screw extruder stage casing, back segment, the flaky lithium iron phosphate forming is not also completed into while stablizing crystal grain, pass into manganese dioxide, mangano-manganic oxide, lithium carbonate manganese dioxide in molar ratio: mangano-manganic oxide: the pre-composition of press=1:0.3:1 of lithium carbonate, calculate according to theoretical value, intake is 55.5% stratiform manganese oxide lithium by weight percentage, the crystal grain of LiFePO4 and manganese oxide lithium is inlayed, and forms by the flaky lithium iron phosphate binary cell positive material alternate with stratiform manganese oxide lithium;
4) at screw extruder end, electric field is set, flaky lithium iron phosphate binary cell positive material under highfield the ion regular arrangement alternate with stratiform manganese oxide lithium that step 3) is obtained, and rapid crystallization, obtain tiny, the uniform LiFePO4-manganese oxide of crystal grain lithium binary anode material of lithium battery.
After testing, LiFePO4-manganese oxide lithium binary anode material of lithium battery at normal temperatures, the specific capacity of battery can reach 251mAh/g, under 1C discharge-rate, through 100 charging cycle, specific capacity can reach 246mAh/g, after 200 5C charge and discharge cycles, the electric specific capacity > 242mAh/g of material, without obviously decay.Material apparent density 1.2g/cm 3, tap density 2.22g/cm 3.
embodiment 3
1) in high-speed mixer by lithium source, source of iron, phosphorus source in molar ratio Li:Fe:P=1:1.2:1 mix, lithium source is lithium dihydrogen phosphate, source of iron is iron chloride, phosphorus source is phosphoric acid, calculate according to theoretical value, get 40 LiFePO4 by weight percentage, 0.8% three oblique crystal C uSO4 are as the agent of crystalline phase growth inducing, 1% sodium thiosulfate, as reducing agent, disperses 3min for subsequent use with the speed high-speed stirred of 4000rpm;
2) mixture obtaining in step 1) is pumped into screw extruder, it is that 60 ° of screwing elements, two groups of oblique angles are the screwing element of 90 ° that screw rod arranges two groups of oblique angles, the screwing element of one group reverse-45 °, the screwing element of a group 45 °, under crystalline phase growth inducing agent effect, the shearing section of the screwing element utilizing forms flaky lithium iron phosphate in dynamic response;
3) at screw extruder stage casing, back segment, the flaky lithium iron phosphate forming is not also completed into while stablizing crystal grain, pass into manganese dioxide, mangano-manganic oxide, lithium carbonate manganese dioxide in molar ratio: mangano-manganic oxide: the pre-composition of press=1:0.4:1 of lithium carbonate, calculate according to theoretical value, intake is 58.2% stratiform manganese oxide lithium by weight percentage, the crystal grain of LiFePO4 and manganese oxide lithium is inlayed, and forms by the flaky lithium iron phosphate binary cell positive material alternate with stratiform manganese oxide lithium;
4) at screw extruder end, electric field is set, flaky lithium iron phosphate binary cell positive material under highfield the ion regular arrangement alternate with stratiform manganese oxide lithium that step 3) is obtained, and rapid crystallization, obtain tiny, the uniform LiFePO4-manganese oxide of crystal grain lithium binary anode material of lithium battery.
After testing, LiFePO4-manganese oxide lithium binary anode material of lithium battery is in the time of 20 DEG C, and the specific capacity of battery can reach 259mAh/g, and has 3.5V stabilised platform voltage; Under 1C discharge-rate, through 100 charging cycle, possess the more than 98% of initial capacity, exceeding in 10C multiplying power discharging situation, without the difference such as blast, distortion, Stability Analysis of Structures, good cycling stability; Apparent density 1.3g/cm 3, tap density 2.35g/cm 3.
embodiment 4
1) in high-speed mixer by lithium source, source of iron, phosphorus source in molar ratio Li:Fe:P=1:1.3:1 mix, lithium source is phosphoric acid hydrogen two lithiums, source of iron is ferric nitrate, add according to theoretical value and calculate, get 41% LiFePO4 by weight percentage, 1% three oblique crystal C uSO4 are as the agent of crystalline phase growth inducing, and 0.5% sodium thiosulfate, as reducing agent, disperses 5min for subsequent use with the speed high-speed stirred of 5000rpm;
2) mixture obtaining in step 1) is pumped into screw extruder, it is that 60 ° of screwing elements, two groups of oblique angles are the screwing element of 90 ° that screw rod arranges two groups of oblique angles, the screwing element of one group reverse-45 °, under crystalline phase growth inducing agent effect, the shearing section of the screwing element utilizing forms flaky lithium iron phosphate in dynamic response;
3) at screw extruder stage casing, back segment, the flaky lithium iron phosphate forming is not also completed into while stablizing crystal grain, pass into manganese dioxide, mangano-manganic oxide, lithium carbonate manganese dioxide in molar ratio: mangano-manganic oxide: the pre-composition of press=1:0.5:1 of lithium carbonate, calculate according to theoretical value, intake is 57.5% stratiform manganese oxide lithium by weight percentage, the crystal grain of LiFePO4 and manganese oxide lithium is inlayed, and forms by the flaky lithium iron phosphate binary cell positive material alternate with stratiform manganese oxide lithium;
4) at screw extruder end, electric field is set, flaky lithium iron phosphate binary cell positive material under highfield the ion regular arrangement alternate with stratiform manganese oxide lithium that step 3) is obtained, and rapid crystallization, obtain tiny, the uniform LiFePO4-manganese oxide of crystal grain lithium binary anode material of lithium battery.
After testing: LiFePO4-manganese oxide lithium binary anode material of lithium battery is uniformly dispersed tiny, D 50for 1-3 μ m.DEG C be that conductivity exceedes 10 in low temperature-20 -6s/cm.
embodiment 5
1) in high-speed mixer by lithium source, source of iron, phosphorus source in molar ratio Li:Fe:P=1:1.2:1 mix, described lithium source is phosphoric acid hydrogen two lithiums, described source of iron is ferric phosphate, described phosphorus source is ammonium dihydrogen phosphate, calculate according to theoretical value, get 42% LiFePO4 by weight percentage, 0.5% three oblique crystal C uSO4 are as the agent of crystalline phase growth inducing, 0.5% sodium thiosulfate, as reducing agent, disperses 5min for subsequent use with the speed high-speed stirred of 1400rpm;
2) mixture obtaining in step 1) is pumped into screw extruder, it is that 60 ° of screwing elements, two groups of oblique angles are the screwing element of 90 ° that screw rod arranges two groups of oblique angles, the screwing element of one group reverse-45 °, the screwing element of a group 45 °, under crystalline phase growth inducing agent effect, the shearing section of the screwing element utilizing forms flaky lithium iron phosphate in dynamic response;
3) at screw extruder stage casing, back segment, the flaky lithium iron phosphate forming is not also completed into while stablizing crystal grain, pass into manganese dioxide, mangano-manganic oxide, lithium carbonate manganese dioxide in molar ratio: mangano-manganic oxide: the pre-composition of press=1:0.3:1 of lithium carbonate, calculate according to theoretical value, intake is 57% stratiform manganese oxide lithium by weight percentage, the crystal grain of LiFePO4 and manganese oxide lithium is inlayed, and forms by the flaky lithium iron phosphate binary cell positive material alternate with stratiform manganese oxide lithium;
4) at screw extruder end, electric field is set, flaky lithium iron phosphate binary cell positive material under highfield the ion regular arrangement alternate with stratiform manganese oxide lithium that step 3) is obtained, and rapid crystallization, obtain tiny, the uniform LiFePO4-manganese oxide of crystal grain lithium binary anode material of lithium battery.
Test through BET method: LiFePO4-manganese oxide lithium binary anode material of lithium battery specific area is 15-20m 2/ g.

Claims (4)

1. a preparation method for LiFePO4-manganese oxide lithium binary anode material of lithium battery, is characterized in that: by LiFePO4 (LiFePO 4), stratiform manganese oxide lithium (LiMnO 2), by crystalline phase induce, shear section and the regular ion of highfield form a kind of layer alternate be LiFePO4-manganese oxide lithium binary anode material of lithium battery that crystal grain is inlayed, wherein LiFePO4 can select conventional lithium source, source of iron, phosphorus source to carry out premixed according to certain mol ratio, manganese oxide lithium can select conventional manganese source, lithium source premixed according to certain mol ratio, and concrete preparation method comprises the following steps:
1) by the Li:Fe:P=1:1.2-1.3:1 mixing in molar ratio of lithium source, source of iron, phosphorus source, composition LiFePO4 initial feed, calculate according to theoretical value, get the LiFePO4 of 40-45% by weight percentage, the three oblique crystal C uSO4 of 0.2-1% are as the agent of crystalline phase growth inducing, the sodium thiosulfate of 0.5-1%, as reducing agent, disperses 3-5min for subsequent use with the speed high-speed stirred of 1400-5000rpm in high-speed mixer;
2) mixture obtaining in step 1) is pumped into screw extruder, it is that 60 ° of screwing elements, two groups of oblique angles are the screwing element of 90 °, the screwing element of a group reverse-45 ° that screw rod arranges two groups of oblique angles, under crystalline phase growth inducing agent effect, utilize the shearing section of screwing element, in dynamic response, form flaky lithium iron phosphate;
3) at screw extruder stage casing, back segment, the flaky lithium iron phosphate forming is not also completed into while stablizing crystal grain, pass into manganese dioxide, mangano-manganic oxide, lithium carbonate manganese dioxide in molar ratio: mangano-manganic oxide: the pre-composition of press=1:0.2-0.5:1 of lithium carbonate, calculate according to theoretical value, intake is the stratiform manganese oxide lithium of 54-59% by weight percentage, section is not induced and sheared to LiFePO4, manganese oxide lithium by crystalline phase when complete crystallization, crystal grain is progressively inlayed, and forms by the flaky lithium iron phosphate binary cell positive material alternate with stratiform manganese oxide lithium;
4) at screw extruder end, electric field polarization is set, flaky lithium iron phosphate binary cell positive material under highfield the ion regular arrangement alternate with stratiform manganese oxide lithium that step 3) is obtained, and rapid crystallization, obtain tiny, the uniform LiFePO4-manganese oxide of crystal grain lithium binary anode material of lithium battery.
2. the preparation method of a kind of LiFePO4-manganese oxide lithium binary anode material of lithium battery as claimed in claim 1, it is characterized in that preparation process 2) described screw extruder is parallel dual-screw extruder, screw slenderness ratio is greater than 65/1, it is characterized in that being provided with shearing screwing element, screwing element oblique angle is the combination of 30 °, 45 °, 60 °, 90 ° ,-45 °, and it is that 60 ° of screwing elements, two groups of oblique angles are that the screwing element of 90 °, the screwing element of a group reverse-45 ° are necessary that two groups of oblique angles are wherein set.
3. the preparation method of a kind of LiFePO4-manganese oxide lithium binary anode material of lithium battery as claimed in claim 1, it is characterized in that preparation process 2), 3), 4) described in screw extruder, adopt confined reaction, the control temperature of its front end, stage casing, back segment, end is: front end 80-100 DEG C, stage casing 150-200 DEG C, back segment 200-240 DEG C, end 250-300 DEG C, screw speed is controlled at 50-120rpm.
4. the preparation method of a kind of LiFePO4-manganese oxide lithium binary anode material of lithium battery as claimed in claim 1, it is characterized in that preparation process 4) described in electric field strength be 100-200KV/m, make LiFePO4-manganese oxide lithium binary cell positive material cation polarization Regularization, and rapid crystallization.
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CN105206805A (en) * 2015-08-31 2015-12-30 无锡市嘉邦电力管道厂 Lithium sulfur battery positive electrode material preparing method and lithium sulfur battery prepared by using lithium sulfur battery positive electrode material
CN106450302A (en) * 2016-11-04 2017-02-22 成都新柯力化工科技有限公司 Lithium ferric manganese phosphate-tungsten disulfide nanometer lithium cell positive material and preparation method thereof
CN107240689A (en) * 2017-06-16 2017-10-10 成都新柯力化工科技有限公司 A kind of dynamic lithium battery manganese oxide lithium bismuth titanates material and preparation method thereof

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CN101369650A (en) * 2007-08-16 2009-02-18 德固赛（中国）投资有限公司 Production method for lithium ion battery material

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CN105206805A (en) * 2015-08-31 2015-12-30 无锡市嘉邦电力管道厂 Lithium sulfur battery positive electrode material preparing method and lithium sulfur battery prepared by using lithium sulfur battery positive electrode material
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CN107240689B (en) * 2017-06-16 2018-12-18 新昌县鼎瑞科技有限公司 A kind of dynamic lithium battery manganese oxide lithium-bismuth titanates material and preparation method thereof

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