CN105914349A - Cupric fluoride-ferric fluoride composite positive electrode material having gradient coatings and used for lithium battery and preparation method thereof - Google Patents

Cupric fluoride-ferric fluoride composite positive electrode material having gradient coatings and used for lithium battery and preparation method thereof Download PDF

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CN105914349A
CN105914349A CN201610209887.4A CN201610209887A CN105914349A CN 105914349 A CN105914349 A CN 105914349A CN 201610209887 A CN201610209887 A CN 201610209887A CN 105914349 A CN105914349 A CN 105914349A
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fluoride
ball milling
positive electrode
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salt
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方敏华
水淼
李月
陈超
李弯弯
舒杰
任元龙
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Ningbo University
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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
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/582—Halogenides
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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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Abstract

The invention provides a Fe2O3/FeF3-2xOx gradiently-coated cupric fluoride-ferric fluoride two-component composite positive electrode material of a lithium battery and a preparation method thereof. According to the method, the cupric fluoride-ferric fluoride two-component composite positive electrode material is prepared by using a solid-phase preparation method with polyquaternary ammonium salts with different structures as templates; then on the basis of the characteristic that FeF3 is prone to gradual oxidation into Fe2O3 at a high temperature, FeF3-2xOx (wherein 0<x<0.3) and a Fe2O3 layer successively coat the cupric fluoride-ferric fluoride two-component composite positive electrode material so as to improve surface electron conduction capability of the cupric fluoride-ferric fluoride two-component composite positive electrode material and to resist harmful effect of an organic electrolyte on particle surfaces of the material; and thus, the comprehensive electrochemical performance of the cupric fluoride-ferric fluoride two-component composite positive electrode material is greatly improved.

Description

A kind of copper fluoride ferric flouride complex lithium electricity positive electrode with Gradient Coated layer and preparation method thereof
Technical field
The present invention relates to a kind of high-performance copper fluoride ferric flouride complex lithium electricity positive electrode manufacture method technical field.
Background technology
Lithium rechargeable battery have volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, the circulation longevity Life is long, the high absolute advantage of power density, has more than 30,000,000,000 dollar/year shares at present in portable power source market, the whole world and with super Cross the speed of 10% gradually to increase.The most in recent years, along with petering out of fossil energy, solar energy, wind energy, biology The new forms of energy such as mass-energy are increasingly becoming the alternative of traditional energy, and wherein wind energy, solar energy have intermittence, continue for meeting Supply of electric power need to use substantial amounts of energy-storage battery simultaneously；The urban air-quality problem that vehicle exhaust brings is day by day serious, Instant stage has been arrived in vigorously advocating and developing of electric motor car (EV) or hybrid electric vehicle (HEV)；These demands provide Lithium ion battery explosive growth point, also has higher requirement to the performance of lithium ion battery simultaneously.
The raising of the capacity of anode material for lithium-ion batteries is the primary goal that scientific and technical personnel study, the research and development of high power capacity positive electrode Can alleviate that current Li-ion batteries piles volume is big, heavy weight, price are high-leveled and difficult to meet high power consumption and the office of high-power equipment needs Face.But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time at 100-180mAh/g Between, positive electrode specific capacity is low has become as the bottleneck promoting lithium ion battery specific energy.At present commercial lithium ion battery is It is LiCoO for positive electrode practical widely2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and actual specific capacity exists Between 130-140mAh/g, and cobalt is strategic materials, expensive and have bigger toxicity.The most in recent years, countries in the world Research worker be devoted to the research and development of Olivine-type Cathode Material in Li-ion Batteries, up till now, the lithium-ion electric filtered out always The most tens of kinds of pond positive pole, but really have potential commercial applications prospect or the positive electrode that is already present on market the most very Lack.Such as lithium manganate having spinel structure LiMn2O4, its cost is relatively low, is easier preparation, and security performance is relatively good, but Capacity is relatively low, and theoretical capacity is 148mAh/g, and actual capacity is at 100-120mAh/g, and the circulation of this material capacity keeps energy Power is the best, and under high temperature, capacity attenuation is quickly, Mn3+John-Teller effect and dissolving in the electrolyte annoying for a long time and grind Study carefully personnel.The LiNiO of layer structure2And LiMnO2Although having bigger theoretical specific capacity, respectively 275mAh/g and 285 MAh/g, but they prepare extremely difficult, poor heat stability, and cyclicity is very poor, and capacity attenuation is quickly.And at present the most by Walk business-like LiFePO4 LiFePO4Low cost, Heat stability is good, environmental friendliness, but its theoretical capacity about only 170 MAh/g, and actual capacity about 140mAh/g [Chun SY, Bloking J T, Chiang Y M, Nature Materials, 2002,1:123-128.].The positive electrode more than 200mAh/g specific capacity having market prospect at present only has lithium vanadate Li1+xV3O8, Li1+xV3O8Material can have and has even close to the capacity of 300mAh/g, but its electric discharge average voltage is relatively low and vanadium in production process Oxide often toxicity is bigger.The highest lithium ratio is on positive electrode, particularly manganio manganese-nickel binary and manganio manganese-nickel-cobalt ternary The high lithium of system solid solution, than positive electrode, has the Capacity Ratio more than 200mAh/g, higher heat stability becomes with relative moderate Originally paid close attention to by people, but the performance under this material high magnification is the most undesirable, limited its answering in electrokinetic cell With [Young-Sik Hong, Yong Joon Park, et al., Solid State Ionics, 2005,176:1035-1042].
In recent years, fluoride positive electrode is owing to its capacity is high, the prices of raw materials are low and enter the visual field of researcher.Fluoride Material is different with the operation principle of conventional lithium ion battery positive electrode, and traditional lithium ion cell positive and negative pole all exist Lithium ion can embed or the space of deintercalation, and the lithium ion in electrolyte embed the most back and forth and deintercalation and put " rocking chair " battery that electricity is proposed as Armand etc..Fluoride is then a kind of transition material, namely in whole electric discharge During, although Me has nothing in common with each other, MeFnSimilar following change [Badway F, Cosandey F, PereiraN, et can occur Al., Electrodes for Li Batteries, J.Electrochem.Soc., 2003,150 (10): A1318-A1327.]:
nLi++MeFn+ne-→nLiF+Me0
Can discharge in this process and exceed well over 200mAh.g-1Specific capacity, thus obtain investigation of materials personnel height weight Depending on.But, all kinds of fluoride positive electrodes are respectively arranged with feature and the shortcoming of oneself, and on the whole, fluoride positive electrode is to crystallization Water is very sensitive, and a small amount of water of crystallization may but be fatal on the impact of chemical property；Additionally fluoride positive electrode is flat All discharge potential ratios are relatively low, lack discharge voltage plateau, thus cause energy density ratio relatively low, and power is smaller；Also have mostly The fluoride of number stability in organic electrolyte is poor, is repeatedly easily caused the change of structure after circulation and circulation is held Amount holding capacity is the best；The synthetic method of conventional fluoride is at high temperature with hydrogen fluoride gas and metal-oxide/hydroxide Or fluorine gas reacts with metal simple-substance, process conditions are harsh, and equipment requirements is the highest, and energy consumption is high, and therefore price is much more expensive； Last most fluoride positive electrode is electronic body, and electronic conductivity is extremely low, therefore can cause in charge and discharge process The highest polarizing voltage.But also there are some fluorides to have prominent advantage, such as copper fluoride to have the discharge platform of up to 3.2V； The water of crystallization that the advantage of ferric flouride is a small amount of has no effect on its chemical property, is also possible in some cases promote its electricity in turn Chemical property, and the reserves that ferrum is in the earth's crust are the abundantest.Generally ion doping, surface coating modification are effective reconciliation statements Face microstructure, changes material electronics and the means of ionic transport properties, it is possible to improve the chemical property of material.But it is electric Pond material is after experience repeatedly circulation, owing to covering material and the lattice mismatch of fertile material and fertile material are in cyclic process Change in volume and cause covering material to lose efficacy from the disengaging of fertile material.The compound of Different electrodes material is also likely to be a kind of performance The respective advantage of material and overcome respective shortcoming, thus improve a kind of means of comprehensive electrochemical, but composite energy No performance better performance has close relationship toward contact with preparation method, the pattern of respective component and structure, is not inevitable.
Therefore develop that a kind of technique is simple, constant product quality, there is the composite fluoride positive electrode system of excellent electrochemical performance Preparation Method is the key that fluoride materials is applied as secondary cell.
Summary of the invention
The present invention is directed to existing background technology and propose a kind of Fe2O3|FeF3-2xOxGradient Coated copper fluoride ferric flouride double-component is multiple Closing lithium electricity positive electrode and preparation method, it is double that the method prepares copper fluoride ferric flouride with the polyquaternary ammonium salt of different structure for template solid phase Component composite positive pole, the lattice both having avoided iron ion and copper ion to enter mutually the other side forms doping, also avoids bulky grain fluorine Change ferrum component and copper fluoride component flocks together, and be so that ferric flouride component and the copper fluoride component chi with nanometer to submicron Degree is the most staggered to flock together, and has both retained the characteristic of each component self, can interact again, has improved its shortcoming.Basis simultaneously FeF3Easily progressively it is oxidized into Fe at relatively high temperatures2O3Characteristic, at copper fluoride ferric flouride double-component composite positive pole FeF it is coated with successively outside granule3-2xOx, 0 ＜ x ＜ 0.3, and Fe2O3Layer is to improve copper fluoride ferric flouride double-component composite positive pole Grain surface electronic conductive capability and resist the organic electrolyte illeffects to material granule surface；In clad, containing of oxygen Amount changes gradually, formation gradient-structure, thus the clad significantly improving material change in volume in cyclic process and causing Come off；Thus increase substantially its comprehensive electrochemical.
This Fe2O3|FeF3-2xOxGradient Coated copper fluoride ferric flouride double-component complex lithium electricity positive electrode and preparation method, it is special Levy for: by mantoquita, the polyquaternary ammonium salt-15 that volume ratio is 1: 1 of mantoquita quality 0.5-5% and the mixture of polyquaternary ammonium salt-28, copper The glycerol of salt quality 0.5-5% and ethylene glycol put into ball mill, ball milling and thing with after mixing liquid mixing that volume ratio is 1: 1 The mass ratio of material is 20: 1, with speed ball milling 3-6 hour of 200-400 rev/min, takes out material, and claim this after ball milling Material is material I；By iron salt, the polyquaternary ammonium salt-7 that volume ratio is 1: 1 of iron salt quality 0.5-5% and the mixing of Polyquaternium-10 Thing, the glycerol of iron salt quality 0.5-5% and ethylene glycol put into ball mill, ball milling with after mixing liquid mixing that volume ratio is 1: 1 Son and the mass ratio of material are 20: 1, with speed ball milling 3-6 hour of 200-400 rev/min, take out material after ball milling, And this material is called material II；By the amount of mantoquita material in material I that mass ratio is 1: 0.7-1.3 and material II, material I and material Putting into ball mill in II after the ammonium fluoride mixing of amount sum 3.0-3.6 times of iron salt material, ball milling is 20: 1 with the mass ratio of material, With speed ball milling 10-20 hour of 200-400 rev/min, take out material after ball milling and this material is called material III；By thing The iron salt that amount ratio is 1: 3.0-3.6 of matter and ammonium fluoride, quality are the material III of iron salt and ammonium fluoride gross mass 80-170 times, ferrum The quaternary ammonium salt with fluorine as anion of the 2-10% of salt and ammonium fluoride gross mass, quality as iron salt, ammonium fluoride and material III gross mass Putting into ball mill after the dehydrated alcohol mixing of 0.5-4%, ball milling is 20: 1 with the mass ratio of material, with 300-500 rev/min Speed ball milling takes out material after 10-20 hour, after three times are washed, be dried 10-20 hour in 100 DEG C of-120 DEG C of drying baker After put in tube furnace, being passed through flow is 1-10L h-1The oxygen that volume ratio is 10: 90 and argon mixed gas, with 2-10 DEG C/ Minute speed be warmed up to 180-260 DEG C and at this temperature keep 15-36 minute；An air gas is i.e. put into after being taken out by this material Atmosphere, temperature constant are to keep the 10-30 second in the Muffle furnace of 800 DEG C, then take out and are cooled to room temperature system under room temperature in argon gas atmosphere Obtain Fe2O3|FeF3-2xOxGradient Coated copper fluoride ferric flouride double-component complex lithium electricity positive electrode.
Mantoquita in preparation method as above is the one in copper sulfate pentahydrate, Gerhardite；Iron salt is nine hydrations One in ferric nitrate, Iron(III) chloride hexahydrate；Quaternary ammonium salt with fluorine as anion is tetra-n-butyl ammonium fluoride, tetramethyl fluorination One in ammonium, benzyl trimethyl ammonium fluoride.
Fig. 1 is charging capacity, discharge capacity and the efficiency for charge-discharge figure of front 10 circulations of this material, voltage range 1.8V-4.0V, Charging and discharging currents 0.5C.
Compared with prior art, it is an advantage of the current invention that: prepare copper fluoride fluorine with the polyquaternary ammonium salt of different structure for template solid phase Changing ferrum double-component composite positive pole, the lattice both having avoided iron ion and copper ion to enter mutually the other side forms doping, also avoids big Granule ferric flouride component and copper fluoride component flock together, and be so that ferric flouride component and copper fluoride component with nanometer to sub-micro The yardstick of rice is closely staggered to flock together, and has both retained the characteristic of each component self, can interact again, has improved its shortcoming.With Time according to FeF3Easily progressively it is oxidized into Fe at relatively high temperatures2O3Characteristic, compound just in copper fluoride ferric flouride double-component FeF it is coated with successively outside the material granule of pole3-2xOx, 0 ＜ x ＜ 0.3, and Fe2O3Layer is to improve copper fluoride ferric flouride double-component anode composite The surface electronic conductive capability of material granule and resist the organic electrolyte illeffects to material granule surface；In clad, The content of oxygen changes gradually, forms gradient-structure, thus significantly improves material change in volume in cyclic process and cause Clad comes off；Thus increase substantially its comprehensive electrochemical.
Accompanying drawing explanation
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of front 10 circulations of this material of Fig. 1, voltage range 1.8V-4.0V, Charging and discharging currents 0.5C.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: by copper sulfate pentahydrate, the polyquaternary ammonium salt that volume ratio is 1: 1-15 of copper sulfate pentahydrate quality 0.6% and poly- The mixture of quaternary ammonium salt-28, the glycerol of copper sulfate pentahydrate quality 0.6% and ethylene glycol are with mixing liquid that volume ratio is 1: 1 Putting into ball mill after mixing, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 3 hours of 210 revs/min, ball milling After take out material, and this material is called material I；By Fe(NO3)39H2O, the volume ratio of Fe(NO3)39H2O quality 0.8% Be 1: 1 polyquaternary ammonium salt-7 and the mixture of Polyquaternium-10, the glycerol of Fe(NO3)39H2O quality 0.8% and ethylene glycol with Volume ratio be 1: 1 mixing liquid mixing after put into ball mill, ball milling is 20: 1 with the mass ratio of material, with 220 revs/min Speed ball milling 3 hours, take out material after ball milling, and this material be called material II；By the material I that mass ratio is 1: 0.7 With the amount of copper sulfate pentahydrate material in material II, material I and the amount sum 3.1 times of Fe(NO3)39H2O material in material II Putting into ball mill after ammonium fluoride mixing, ball milling is 20: 1 with the mass ratio of material, and the speed ball milling 10 with 220 revs/min is little Time, take out material after ball milling and this material is called material III；By Fe(NO3)39H2O and the fluorine that amount ratio is 1: 3.1 of material Change ammonium, quality is Fe(NO3)39H2O and the material III of ammonium fluoride gross mass 85 times, Fe(NO3)39H2O and ammonium fluoride gross mass 2.1% tetra-n-butyl ammonium fluoride, quality be Fe(NO3)39H2O, ammonium fluoride and the dehydrated alcohol of material III gross mass 0.6% Putting into ball mill after mixing, ball milling is 20: 1 with the mass ratio of material, takes after 10 hours with the speed ball millings of 320 revs/min Going out material, after three times are washed, put in tube furnace after being dried 10 hours in 100 DEG C of drying baker, being passed through flow is 2L h-1 The oxygen that volume ratio is 10: 90 and argon mixed gas, be warmed up to 190 DEG C with the speed of 2 DEG C/min and protect at this temperature Hold 15 minutes；I.e. put into an air atmosphere after being taken out by this material, temperature constant is to keep 12 seconds in the Muffle furnace of 800 DEG C, Then take out and in argon gas atmosphere, be cooled to room temperature under room temperature prepare Fe2O3|FeF3-2xOxThe double group of Gradient Coated copper fluoride ferric flouride Part complex lithium electricity positive electrode.
Embodiment 2: by copper sulfate pentahydrate, the polyquaternary ammonium salt that volume ratio is 1: 1-15 of copper sulfate pentahydrate quality 2.5% and poly- The mixture of quaternary ammonium salt-28, the glycerol of copper sulfate pentahydrate quality 2.5% and ethylene glycol are with mixing liquid that volume ratio is 1: 1 Putting into ball mill after mixing, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 4 hours of 300 revs/min, ball milling After take out material, and this material is called material I；By Fe(NO3)39H2O, the volume ratio of Fe(NO3)39H2O quality 3.2% Be 1: 1 polyquaternary ammonium salt-7 and the mixture of Polyquaternium-10, the glycerol of Fe(NO3)39H2O quality 3.2% and ethylene glycol with Volume ratio be 1: 1 mixing liquid mixing after put into ball mill, ball milling is 20: 1 with the mass ratio of material, with 320 revs/min Speed ball milling 4 hours, take out material after ball milling, and this material be called material II；By the material I that mass ratio is 1: 1 With the amount of copper sulfate pentahydrate material in material II, material I and the amount sum 3.3 times of Fe(NO3)39H2O material in material II Putting into ball mill after ammonium fluoride mixing, ball milling is 20: 1 with the mass ratio of material, and the speed ball milling 15 with 320 revs/min is little Time, take out material after ball milling and this material is called material III；By Fe(NO3)39H2O and the fluorine that amount ratio is 1: 3.2 of material Change ammonium, quality is Fe(NO3)39H2O and the material III of ammonium fluoride gross mass 125 times, Fe(NO3)39H2O and ammonium fluoride gross mass 5% tetra-n-butyl ammonium fluoride, quality be Fe(NO3)39H2O, the dehydrated alcohol of ammonium fluoride and material III gross mass 2% mix Putting into ball mill after conjunction, ball milling is 20: 1 with the mass ratio of material, takes out after 16 hours with the speed ball millings of 400 revs/min Material, after three times are washed, puts in tube furnace after being dried 16 hours in 110 DEG C of drying baker, and being passed through flow is 6L h-1 The oxygen that volume ratio is 10: 90 and argon mixed gas, be warmed up to 220 DEG C with the speed of 6 DEG C/min and protect at this temperature Hold 25 minutes；I.e. put into an air atmosphere after being taken out by this material, temperature constant is to keep 20 seconds in the Muffle furnace of 800 DEG C, Then take out and in argon gas atmosphere, be cooled to room temperature under room temperature prepare Fe2O3|FeF3-2xOxThe double group of Gradient Coated copper fluoride ferric flouride Part complex lithium electricity positive electrode.
Embodiment 3: by copper sulfate pentahydrate, the polyquaternary ammonium salt that volume ratio is 1: 1-15 of copper sulfate pentahydrate quality 5% and poly- The mixture of quaternary ammonium salt-28, the glycerol of copper sulfate pentahydrate quality 5% and ethylene glycol mix with the mixing liquid that volume ratio is 1: 1 Putting into ball mill after conjunction, ball milling is 20: 1 with the mass ratio of material, and with the speed ball milling 6 hours of 400 revs/min, ball milling is complete Take out material after Biing, and this material is called material I；It is 1: 1 by the volume ratio of Fe(NO3)39H2O, Fe(NO3)39H2O quality 5% Polyquaternary ammonium salt-7 and the mixture of Polyquaternium-10, the glycerol of Fe(NO3)39H2O quality 5% and ethylene glycol with volume ratio be Putting into ball mill after the mixing liquid mixing of 1: 1, ball milling is 20: 1 with the mass ratio of material, with the speed ball of 400 revs/min Grind 6 hours, after ball milling, take out material, and this material is called material II；By material I that mass ratio is 1: 1.3 and material II, In material I, the amount of copper sulfate pentahydrate material mixes with the ammonium fluoride of the amount sum of Fe(NO3)39H2O material 3.6 times in material II After put into ball mill, ball milling is 20: 1 with the mass ratio of material, and with the speed ball milling 20 hours of 400 revs/min, ball milling is complete Take out material after Biing and this material is called material III；By the Fe(NO3)39H2O that amount ratio is 1: 3.6 and ammonium fluoride, the quality of material For the 8% of Fe(NO3)39H2O and the material III of ammonium fluoride gross mass 150 times, Fe(NO3)39H2O and ammonium fluoride gross mass four Methyl ammonium fluoride, quality are Fe(NO3)39H2O, put into ball milling after the dehydrated alcohol mixing of ammonium fluoride and material III gross mass 4% Machine, ball milling is 20: 1 with the mass ratio of material, takes out material, Jing Guosan with the speed ball millings of 500 revs/min after 20 hours After secondary washing, putting in tube furnace after being dried 20 hours in 120 DEG C of drying baker, being passed through flow is 10L h-1Volume ratio be The oxygen of 10: 90 and argon mixed gas, be warmed up to 260 DEG C with the speed of 10 DEG C/min and keep 30 minutes at this temperature； I.e. put into an air atmosphere after being taken out by this material, temperature constant is to keep 30 seconds in the Muffle furnace of 800 DEG C, then takes out at argon Gas atmosphere is cooled to room temperature under room temperature and prepares Fe2O3|FeF3-2xOxGradient Coated copper fluoride ferric flouride double-component complex lithium electricity is just Pole material.
Embodiment 4: by Gerhardite, the polyquaternary ammonium salt that volume ratio is 1: 1-15 of Gerhardite quality 1.5% and poly- The mixture of quaternary ammonium salt-28, the glycerol of Gerhardite quality 1.5% and ethylene glycol are with mixing liquid that volume ratio is 1: 1 Putting into ball mill after mixing, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 5 hours of 320 revs/min, ball milling After take out material, and this material is called material I；By Iron(III) chloride hexahydrate, the body of Iron(III) chloride hexahydrate quality 2.2% Long-pending than the polyquaternary ammonium salt-7 and the mixture of Polyquaternium-10, the glycerol of Iron(III) chloride hexahydrate quality 2.2% and the second that are 1: 1 Glycol is to put into ball mill after mixing liquid mixing that volume ratio is 1: 1, ball milling is 20: 1 with the mass ratio of material, with 320 Rev/min speed ball milling 5 hours, take out material after ball milling, and this material be called material II；It is 1: 1.2 by mass ratio Material I and material II, material I in Gerhardite material amount and material II in Iron(III) chloride hexahydrate material amount it Putting into ball mill after ammonium fluoride mixing with 3.3 times, ball milling is 20: 1 with the mass ratio of material, with the speed of 320 revs/min Ball milling 15 hours, takes out material after ball milling and this material is called material III；By amount ratio is 1: 3.4 six hydrations three of material Iron chloride and ammonium fluoride, quality are Iron(III) chloride hexahydrate and the material III of ammonium fluoride gross mass 120 times, Iron(III) chloride hexahydrate With the 6% of ammonium fluoride gross mass Methanaminium, N,N,N-trimethyl-, fluoride, quality be Iron(III) chloride hexahydrate, ammonium fluoride and material III gross mass 3% Dehydrated alcohol mixing after put into ball mill, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 17 of 400 revs/min Take out material after hour, after three times are washed, put in tube furnace after being dried 15 hours in 110 DEG C of drying baker, be passed through stream Amount is 5L h-1The oxygen that volume ratio is 10: 90 and argon mixed gas, with the speed of 5 DEG C/min be warmed up to 220 DEG C and Keep 25 minutes at a temperature of this；I.e. put into an air atmosphere after being taken out by this material, temperature constant is to protect in the Muffle furnace of 800 DEG C Hold 20 seconds, then take out and in argon gas atmosphere, be cooled to room temperature under room temperature prepare Fe2O3|FeF3-2xOxGradient Coated copper fluoride fluorine Change ferrum double-component complex lithium electricity positive electrode.
Embodiment 5: by Gerhardite, the polyquaternary ammonium salt that volume ratio is 1: 1-15 of Gerhardite quality 5% and poly- The mixture of quaternary ammonium salt-28, the glycerol of Gerhardite quality 1.6% and ethylene glycol are with mixing liquid that volume ratio is 1: 1 Putting into ball mill after mixing, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 3 hours of 230 revs/min, ball milling After take out material, and this material is called material I；By Iron(III) chloride hexahydrate, the volume of Iron(III) chloride hexahydrate quality 5% Than the polyquaternary ammonium salt-7 and the mixture of Polyquaternium-10, the glycerol of Iron(III) chloride hexahydrate quality 2.2% and the second two that are 1: 1 Alcohol is to put into ball mill after mixing liquid mixing that volume ratio is 1: 1, ball milling is 20: 1 with the mass ratio of material, with 400 turns/ Minute speed ball milling 5 hours, take out material after ball milling, and this material be called material II；It is the thing of 1: 0.8 by mass ratio The amount of Gerhardite material and the amount sum 3.3 of Iron(III) chloride hexahydrate material in material II in material I and material II, material I Putting into ball mill after ammonium fluoride mixing again, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 15 of 300 revs/min Hour, take out material after ball milling and this material is called material III；It is the Iron(III) chloride hexahydrate of 1: 3.1 by the amount ratio of material It is Iron(III) chloride hexahydrate and material III, Iron(III) chloride hexahydrate and the fluorination of ammonium fluoride gross mass 155 times with ammonium fluoride, quality The benzyl trimethyl ammonium fluoride of the 8% of ammonium gross mass, quality are Iron(III) chloride hexahydrate, ammonium fluoride and material III gross mass 3% Dehydrated alcohol mixing after put into ball mill, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 15 of 400 revs/min Take out material after hour, after three times are washed, put in tube furnace after being dried 16 hours in 100 DEG C of drying baker, be passed through stream Amount is 7L h-1The oxygen that volume ratio is 10: 90 and argon mixed gas, with the speed of 5 DEG C/min be warmed up to 220 DEG C and Keep 25 minutes at a temperature of this；I.e. put into an air atmosphere after being taken out by this material, temperature constant is to protect in the Muffle furnace of 800 DEG C Hold 20 seconds, then take out and in argon gas atmosphere, be cooled to room temperature under room temperature prepare Fe2O3|FeF3-2xOxGradient Coated copper fluoride fluorine Change ferrum double-component complex lithium electricity positive electrode.

Claims (2)

1.Fe2O3|FeF3-2xOxGradient Coated copper fluoride ferric flouride double-component complex lithium electricity positive electrode, it is characterised in that with different structure Polyquaternary ammonium salt be that template solid phase prepares copper fluoride ferric flouride double-component composite positive pole, copper fluoride ferric flouride double-component be combined FeF it is coated with successively outside positive electrode granule3-2xOx, 0 ＜ x ＜ 0.3, and Fe2O3Layer, at FeF3-2xOx, in 0 ＜ x ＜ 0.3 clad, The content of oxygen changes gradually, forms gradient-structure；Preparation process is: be 1: 1 by the volume ratio of mantoquita, mantoquita quality 0.5-5% Polyquaternary ammonium salt-15 and the mixture of polyquaternary ammonium salt-28, the glycerol of mantoquita quality 0.5-5% and ethylene glycol with volume ratio for 1: 1 Mixing liquid mixing after put into ball mill, ball milling is 20: 1 with the mass ratio of material, with the speed ball of 200-400 rev/min Grind 3-6 hour, after ball milling, take out material, and this material is called material I；By iron salt, the volume ratio of iron salt quality 0.5-5% Be 1: 1 polyquaternary ammonium salt-7 and the mixture of Polyquaternium-10, the glycerol of iron salt quality 0.5-5% and ethylene glycol with volume ratio be Putting into ball mill after the mixing liquid mixing of 1: 1, ball milling is 20: 1 with the mass ratio of material, with the speed of 200-400 rev/min Degree ball milling 3-6 hour, takes out material after ball milling, and this material is called material II；By the material I that mass ratio is 1: 0.7-1.3 Put after in material II, the ammonium fluoride of amount sum 3.0-3.6 times of iron salt material mixes with the amount of mantoquita material in material II, material I Entering ball mill, ball milling is 20: 1 with the mass ratio of material, with speed ball milling 10-20 hour of 200-400 rev/min, ball milling After to take out material this material be called material III；It is ferrum by the iron salt that amount ratio is 1: 3.0-3.6 and ammonium fluoride, the quality of material The quaternary ammonium with fluorine as anion of the 2-10% of the material III of salt and ammonium fluoride gross mass 80-170 times, iron salt and ammonium fluoride gross mass Salt, quality are iron salt, put into ball mill after the mixing of the dehydrated alcohol of ammonium fluoride and material III gross mass 0.5-4%, ball milling with The mass ratio of material is 20: 1, to take out material after speed ball milling 10-20 hour of 300-500 rev/min, through three washings After, put in tube furnace after being dried 10-20 hour in 100 DEG C of-120 DEG C of drying baker, being passed through flow is 1-10L h-1Volume ratio It is oxygen and the argon mixed gas of 10: 90, is warmed up to 180-260 DEG C with the speed of 2-10 DEG C/min and keeps at this temperature 15-36 minute；I.e. put into an air atmosphere after being taken out by this material, temperature constant is to keep the 10-30 second in the Muffle furnace of 800 DEG C, Then take out and in argon gas atmosphere, be cooled to room temperature under room temperature prepare Fe2O3|FeF3-2xOxThe double group of Gradient Coated copper fluoride ferric flouride Part complex lithium electricity positive electrode.
Fe the most according to claim 12O3|FeF3-2xOxGradient Coated copper fluoride ferric flouride double-component complex lithium electricity positive electrode, It is characterized in that above-mentioned mantoquita is the one in copper sulfate pentahydrate, Gerhardite；Iron salt be Fe(NO3)39H2O, six One in iron chloride hexahydrate；Quaternary ammonium salt with fluorine as anion is tetra-n-butyl ammonium fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, benzyl three One in methyl ammonium fluoride.
CN201610209887.4A 2016-03-29 2016-03-29 Cupric fluoride-ferric fluoride composite positive electrode material having gradient coatings and used for lithium battery and preparation method thereof Pending CN105914349A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807866A (en) * 2017-04-27 2018-11-13 丰田自动车株式会社 The manufacturing method of electrode active material, fluoride ion all-solid-state battery and electrode active material
CN111900399A (en) * 2020-07-21 2020-11-06 江苏兆维塑料科技有限公司 Micro-nano Fe with non-layered heterostructure2O3/Fe2F5Porous ball lithium battery negative electrode material and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108807866A (en) * 2017-04-27 2018-11-13 丰田自动车株式会社 The manufacturing method of electrode active material, fluoride ion all-solid-state battery and electrode active material
CN108807866B (en) * 2017-04-27 2021-10-19 丰田自动车株式会社 Electrode active material, fluoride ion all-solid-state battery, and method for producing electrode active material
CN111900399A (en) * 2020-07-21 2020-11-06 江苏兆维塑料科技有限公司 Micro-nano Fe with non-layered heterostructure2O3/Fe2F5Porous ball lithium battery negative electrode material and preparation method and application thereof
CN111900399B (en) * 2020-07-21 2022-04-15 江苏兆维塑料科技有限公司 Micro-nano Fe with non-layered heterostructure2O3/Fe2F5Porous ball lithium battery negative electrode material and preparation method and application thereof

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