CN106953083A - A kind of continuous conduction original position C/ metal solid solutions/Ni2+,Ca2+Adulterate BiF3Positive pole and preparation method - Google Patents

A kind of continuous conduction original position C/ metal solid solutions/Ni2+,Ca2+Adulterate BiF3Positive pole and preparation method Download PDF

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CN106953083A
CN106953083A CN201710213006.0A CN201710213006A CN106953083A CN 106953083 A CN106953083 A CN 106953083A CN 201710213006 A CN201710213006 A CN 201710213006A CN 106953083 A CN106953083 A CN 106953083A
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bismuth
aqueous solution
metal solid
adulterate
original position
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姘存芳
水淼
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Ningbo Kyrgyzstan Xin New Mstar Technology Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/582Halogenides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/626Metals
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

A kind of continuous conduction original position C/ metal solid solutions/Ni2+, Ca2+Adulterate BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method thereof; this method passes through the drying process under low temperature, high vacuum condition and the carbonization under gas shield and in-situ reducing process; form the continuous carbon film with hole and gap structure; and fixed formed is fluorinated bismuth and restores a certain amount of metal solid solution in the surface in situ of fluorination bismuth particle on the carbon film, plays the electronic conductivity for increasing substantially composite;Homogeneity crystallization nuclei is provided in electric discharge for electrode material, the dynamics of reduction New phase formation hinders;Ni2+, Ca2+Doping is favorably improved exoelectrical reaction speed;The generation in liquid phase reactor is also avoid simultaneously is fluorinated the side reaction products such as a variety of double salt of bismuth and with excellent chemical property.

Description

A kind of continuous conduction original position C/ metal solid solutions/Ni2+, Ca2+Adulterate BiF3Positive pole and system Preparation Method
Technical field
The present invention relates to a kind of electric positive electrode manufacture method technical field of high-performance fluorination bismuth complex lithium.
Background technology
Lithium rechargeable battery has volume, weight energy higher than high, voltage, low self-discharge rate, memory-less effect, circulation Long lifespan, power density height etc. definitely advantage, had more than at present in global portable power source market 30,000,000,000 dollar/year shares and with Speed more than 10% gradually increases.Particularly in recent years, petering out with fossil energy, solar energy, wind energy, biomass The new energy such as energy are increasingly becoming the alternative of traditional energy, and wherein wind energy, solar energy has intermittence, to meet lasting electricity Power supply needs to use substantial amounts of energy-storage battery simultaneously;The urban air-quality problem that vehicle exhaust is brought is increasingly serious, electronic Very urgent stage has been arrived in vigorously advocating and developing for car (EV) or hybrid electric vehicle (HEV);These demands are provided Lithium ion battery explosive growth point, while also the performance to lithium ion battery proposes higher requirement.
The raising of the capacity of anode material for lithium-ion batteries is the primary goal of scientific and technical personnel's research, high power capacity positive electrode Research and development can to alleviate current Li-ion batteries piles volume big, heavy weight, price high-leveled and difficult to meet high power consumption and high-power equipment The situation needed.But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time Between 100-180mAh/g, the low bottleneck for having become lifting lithium ion battery specific energy of positive electrode specific capacity.It is commercial at present The most commonly used practical positive electrode of lithium ion battery be LiCoO2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and Actual specific capacity is between 130-140mAh/g, and cobalt is strategic materials, expensive and have larger toxicity.Therefore it is near Nian Lai, the researcher of countries in the world is directed to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, to current, sieve Up to tens of kinds of the lithium ion cell positive selected, but really have potential commercial applications prospect or be already present in the market Positive electrode is really very few.Such as lithium manganate having spinel structure LiMn2O4, its cost is relatively low, is easier to prepare, security performance Also it is relatively good, but capacity is relatively low, theoretical capacity is 148mAh/g, and actual capacity is in 100-120mAh/g, and the material holds Amount circulation holding capacity it is not good, under high temperature capacity attenuation quickly, Mn3+John-Teller effects and dissolving in the electrolyte Researcher is annoying for a long time.The LiNiO of layer structure2And LiMnO2Although there is larger theoretical specific capacity, it is respectively 275mAh/g and 285 mAh/g, but they prepare extremely difficult, heat endurance is poor, and cyclicity is very poor, and capacity attenuation is quickly. And progressively commercialized LiFePO4 LiFePO at present4Low cost, heat endurance are good, environment-friendly, but its theory is held Amount about only have 170 mAh/g, and actual capacity 140mAh/g or so [Chun SY, Bloking J T, Chiang Y M, Nature Materials, 2002,1:123-128.].There is the positive pole material more than 200mAh/g specific capacities of market prospects at present Material only has lithium vanadate Li1+xV3O8, Li1+xV3O8Material can have the capacity possessed even close to 300mAh/g, but its electric discharge is average Voltage is relatively low and production process in barium oxide often toxicity is larger.High lithium is than on positive electrode in recent years, particularly manganese base The high lithium of manganese-nickel binary and manganese base manganese-nickel-cobalt ternary solid solution system than positive electrode, with the Capacity Ratio more than 200mAh/g, Higher heat endurance and the cost of relative moderate and paid close attention to by people, but the performance under the material high magnification is very not Ideal, limits its application [Young-Sik Hong, Yong Joon Park, et al., Solid in electrokinetic cell State Ionics, 2005,176:1035-1042].
In recent years, fluoride positive electrode is because its capacity is high, the prices of raw materials are low and enter the visual field of researcher.Fluorine The operation principle of compound material and conventional lithium ion battery positive electrode is different, traditional lithium ion cell positive and negative pole All exist lithium ion can be embedded in or deintercalation space, and lithium ion in electrolyte it is embedded back and forth between a positive electrode and a negative electrode and Deintercalation and " rocking chair " battery proposed as Armand etc. that discharges.And fluoride is then a kind of transition material, that is, whole In individual discharge process, although Me has nothing in common with each other, MeFnCan occur similar following change [Badway F, Cosandey F, PereiraN, et al., Electrodes for Li Batteries, J.Electrochem.Soc., 2003,150 (10): A1318-A1327.]:
nLi++MeFn+ne-→nLiF+Me0
It can discharge in this process and exceed well over 200mAh.g-1Specific capacity, thus it is high to obtain investigation of materials personnel The attention of degree.Wherein fluorination bismuth is due to there is about 7170WhL-1Volume and capacity ratio and have big advantage.Conventional fluorine Change the synthetic method of bismuth to be carried out with metal simple-substance with metal oxide/hydroxide or fluorine gas with hydrogen fluoride gas at high temperature Reaction, process conditions are harsh, and equipment requirement is very high, high energy consumption, therefore price is very expensive.And liquid phase reactor prepares fluorination bismuth Then it can not often be used because by-products content is too high as positive electrode simultaneously because being hydrolyzed to suppress bismuth nitrate in water And the dust technology added has the risk for being acted on ammonium fluoride and producing high toxicity hydrogen fluoride.Bismuth is fluorinated as lithium ion secondary electricity It is that its electronic conductivity is extremely low that pond positive electrode, which also has a negative characteristic, therefore can be caused in charge and discharge process very high Polarizing voltage.Although having researcher improves the electrical conductivity of material using carbon black mixing and ball milling is added, but granular charcoal It is black to be still difficult to form complete electrically conductive links, increase substantially its electronic conductivity.Finally, the material produces gold in electric discharge Belong to bismuth and lithium fluoride cenotype, cenotype small particles are kinetically being on a sticky wicket in the stage that originally forms, therefore to thereafter Charge/discharge capacity, discharge potential, the holding capacity of charge/discharge capacity can have a negative impact.Ion doping is also a kind of effective Regulation lattice microstructure, change the means of lattice electron and ionic transport properties, however, ion doping it is even many from Son collaboration doping is extremely complex to the mechanism of action of parent, and effect is often difficult to expect.
Therefore exploitation one kind has complete conductive link, purity height, technical process is environment-friendly, product quality is stable, tool The compound fluorination bismuth material preparation method for having excellent electrochemical performance is to be fluorinated the key that bismuth material is applied as secondary cell.
The content of the invention
The present invention proposes a kind of continuous conduction original position C/ metal solid solutions/Ni for existing background technology2+, Ca2+Doping BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method thereof, this method passes through dry under low temperature, high vacuum condition Dry process, the reactants such as bismuth nitrate are fixed in the Continuous Polyacrylamide body for maintaining hole and gap structure and passed through Liquid phase reactor in-situ preparation is fluorinated bismuth material, thereafter by the continuous polypropylene with hole and gap structure in heat treatment process Acid amides is integrally transformed into the continuous carbon film with hole and gap structure, and the continuous carbon film structure has high conductive capability, Increase substantially the electronic conductivity of composite;Go out necessarily in the surface reduction of fluorination bismuth particle in heat treatment process simultaneously The metal solid solution of amount, homogeneity crystallization nuclei is provided for electrode material in electric discharge, reduces the dynamics resistance of New phase formation Hinder, improve capacity, circulation volume stability and the discharge platform current potential of material;Ni2+, Ca2+It is anti-that doping is favorably improved electric discharge Answer speed;Pass through the immobilization of reaction raw materials, it is thus also avoided that the side reaction such as a variety of double salt of generation fluorination bismuth in liquid phase reactor Product simultaneously has excellent chemical property.
This continuous conduction original position C/ metal solid solutions/Ni2+, Ca2+Adulterate BiF3Compound fluorination bismuth lithium ion cell positive Material and preparation method thereof, it is characterized in that:It is 5-15wt% bismuth nitrates, 0.1-0.5wt% nickel nitrates, 0.1- to prepare composition 0.5wt% calcium nitrate, 0.5-1wt% nitric acid, 6-12wt% acrylamides, 1-2wt%N, N '-methylene-bisacrylamide The quality of starting aqueous solution, wherein acrylamide is N, 6 times of N '-methylene-bisacrylamide quality, uses polytetrafluoroethylene (PTFE) Agitating paddle is stirred 5-15 minutes with 900rpm-1200rpm speed.By the starting aqueous solution with 5-10 DEG C/min of speed It is raised to 75-85 DEG C and keeps the temperature until starting aqueous solution is as gelatin gel.By the gel of formation in low temperature Gao Zhen Dried in the environment of reciprocal of duty cycle, gel can be put into freezing by the drying process using finished product freeze drier in the market Start refrigeration machine in drying machine sample disc, treat that gelling temp is reduced to subzero 50 DEG C of subzero 45- in sample disc, open vavuum pump and carry Condition of high vacuum degree, treats that gas pressure is reduced to below 25-35Pa in system, opens baffle temperature control and starts to dehydrate, other Operating parameter takes machine preset value, after stable gas pressure drying terminates in system, is saturation by material immersion concentration after drying Concentration 70-90%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 8-20 times of the amount of bismuth nitrate material in starting aqueous solution And stirred 15-30 seconds in the case where Teflon stir oar is with 1000rpm-1200rpm speed, filter thereafter, at 80-120 DEG C Drying box in dry 3-7 hours after 0.5% hydrogen and 99.5% argon gas it is mixed gas protected under be warming up to 450-550 DEG C Constant temperature is cooled down after 0.5-2 hours, prepares continuous conduction original position C/ metal solid solutions/Ni2+, Ca2+Adulterate BiF3Compound fluorination Bismuth anode material for lithium-ion batteries.
Compared with prior art, the advantage of the invention is that:This method passes through dried under low temperature, high vacuum condition Journey, the reactants such as bismuth nitrate are fixed in the Continuous Polyacrylamide body for maintaining hole and gap structure and by liquid phase In-situ preparation fluorination bismuth material is reacted, thereafter by the Continuous Polyacrylamide with hole and gap structure in heat treatment process Entirety is transformed into the continuous carbon film with hole and gap structure, and the continuous carbon film structure has high conductive capability, significantly Degree improves the electronic conductivity of composite;Go out simultaneously in heat treatment process in the surface reduction for being fluorinated bismuth particle a certain amount of Metal solid solution, homogeneity crystallization nuclei is provided for electrode material in electric discharge, and the dynamics for reducing New phase formation hinders, and carries The high capacity of material, circulation volume stability and discharge platform current potential;Ni2+, Ca2+Doping is favorably improved exoelectrical reaction speed Rate;Pass through the immobilization of reaction raw materials, it is thus also avoided that the side reaction product such as a variety of double salt of generation fluorination bismuth in liquid phase reactor And with excellent chemical property.
Brief description of the drawings
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of Fig. 1 materials, voltage range 1.8V- 4.0V, charging and discharging currents 0.1C.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1:It is 5wt% bismuth nitrates, 0.1wt% nickel nitrates, 0.1wt% calcium nitrate, 0.5wt% nitre to prepare composition Acid, 6wt% acrylamides, 1wt%N, N '-methylene-bisacrylamide starting aqueous solution, use Teflon stir oar Stirred 5 minutes with 900rpm speed.The starting aqueous solution is risen to 75 DEG C with 5 DEG C/min of speed and the temperature is kept Until starting aqueous solution turns into gelatin gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying Gel is put into freeze drier sample disc using finished product freeze drier in the market and starts refrigeration machine, treated by process Gelling temp is reduced to subzero 46 DEG C in sample disc, opens vavuum pump and improves vacuum, treats that gas pressure is reduced in system Below 27Pa, opens baffle temperature control and starts to dehydrate, other operating parameters take machine preset value, treat air pressure in system It is stable dry terminate after, be saturated concentration 70% by material immersion concentration after drying, the amount of ammonium fluoride material is starting aqueous solution Stirred in the ammonium fluoride aqueous solution of 8 times of the amount of middle bismuth nitrate material and in the case where Teflon stir oar is with 1100rpm speed 15 seconds, filter thereafter, the mixed gas after being dried 3 hours in 80 DEG C of drying box in 0.5% hydrogen and 99.5% argon gas is protected 450 DEG C of constant temperature are warming up under shield to cool down after 0.5 hour, prepare continuous conduction original position C/ metal solid solutions/Ni2+, Ca2+Mix Miscellaneous BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
Embodiment 2:Prepare composition 15wt% bismuth nitrates, 0.5wt% nickel nitrates, 0.5wt% calcium nitrate, 1wt% nitric acid, 12wt% acrylamides, 2wt%N, N '-methylene-bisacrylamide starting aqueous solution, using Teflon stir oar with 1200rpm speed is stirred 14 minutes.The starting aqueous solution is risen to 85 DEG C with 10 DEG C/min of speed and the temperature is kept Degree turns into gelatin gel until starting aqueous solution.The gel of formation is dried in the environment of low-temperature high-vacuum degree, this is done Gel is put into freeze drier sample disc using finished product freeze drier in the market and is started refrigeration machine by dry process, Treat that gelling temp is reduced to subzero 50 DEG C in sample disc, open vavuum pump and improve vacuum, treat that gas pressure is reduced in system Below 34Pa, opens baffle temperature control and starts to dehydrate, other operating parameters take machine preset value, treat air pressure in system It is stable dry terminate after, be saturated concentration 88% by material immersion concentration after drying, the amount of ammonium fluoride material is starting aqueous solution Stirred in the ammonium fluoride aqueous solution of 20 times of the amount of middle bismuth nitrate material and in the case where Teflon stir oar is with 1200rpm speed Mix 30 seconds, filter thereafter, in 0.5% hydrogen and the gaseous mixture of 99.5% argon gas after being dried 7 hours in 115 DEG C of drying box 550 DEG C of constant temperature are warming up under body protection to cool down after 2 hours, prepare continuous conduction original position C/ metal solid solutions/Ni2+, Ca2+ Adulterate BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
Embodiment 3:It is 12wt% bismuth nitrates, 0.3wt% nickel nitrates, 0.3wt% calcium nitrate, 0.8wt% nitre to prepare composition Acid, 9wt% acrylamides, 1.5wt%N, N '-methylene-bisacrylamide starting aqueous solution, use Teflon stir Oar is stirred 9 minutes with 1100rpm speed.The starting aqueous solution is risen to 80 DEG C with 7 DEG C/min of speed and keeps being somebody's turn to do Temperature turns into gelatin gel until starting aqueous solution.The gel of formation is dried in the environment of low-temperature high-vacuum degree, should Gel is put into start in freeze drier sample disc and freezed by drying process using finished product freeze drier in the market Machine, treats that gelling temp is reduced to subzero 48 DEG C in sample disc, opens vavuum pump and improve vacuum, treats that gas pressure is reduced in system To below 30Pa, open baffle temperature control and start to dehydrate, other operating parameters take machine preset value, treat gas in system Pressure is stable dry and terminate after, be saturated concentration 80% by material immersion concentration after drying, the amount of ammonium fluoride material is water-soluble to originate With under 1150rpm speed in the ammonium fluoride aqueous solution of 15 times of the amount of bismuth nitrate material and in Teflon stir oar in liquid Stirring 25 seconds, is filtered thereafter, in the mixing of 0.5% hydrogen and 99.5% argon gas after being dried 5 hours in 100 DEG C of drying box 500 DEG C of constant temperature are warming up under gas shield to cool down after 1 hour, prepare continuous conduction original position C/ metal solid solutions/Ni2+, Ca2+Adulterate BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
Embodiment 4:Prepare composition for 5wt% bismuth nitrates, 0.4wt% nickel nitrates, 0.1wt% calcium nitrate, 1wt% nitric acid, 12wt% acrylamides, 2wt%N, N '-methylene-bisacrylamide starting aqueous solution, using Teflon stir oar with 1000rpm speed is stirred 10 minutes.The starting aqueous solution is risen to 80 DEG C with 7 DEG C/min of speed and the temperature is kept Until starting aqueous solution turns into gelatin gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying Gel is put into freeze drier sample disc using finished product freeze drier in the market and starts refrigeration machine, treated by process Gelling temp is reduced to subzero 48 DEG C in sample disc, opens vavuum pump and improves vacuum, treats that gas pressure is reduced in system Below 30Pa, opens baffle temperature control and starts to dehydrate, other operating parameters take machine preset value, treat air pressure in system It is stable dry terminate after, be saturated concentration 80% by material immersion concentration after drying, the amount of ammonium fluoride material is starting aqueous solution Stirred in the ammonium fluoride aqueous solution of 8 times of the amount of middle bismuth nitrate material and in the case where Teflon stir oar is with 1150rpm speed 22 seconds, filter thereafter, in the mixed gas of 0.5% hydrogen and 99.5% argon gas after being dried 5 hours in 110 DEG C of drying box 480 DEG C of constant temperature are warming up under protection to cool down after 1 hour, prepare continuous conduction original position C/ metal solid solutions/Ni2+, Ca2+Mix Miscellaneous BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
Embodiment 5:It is 7.5wt% bismuth nitrates, 0.1wt% nickel nitrates, 0.2wt% calcium nitrate, 0.7wt% nitre to prepare composition Acid, 9wt% acrylamides, 1.5wt%N, N '-methylene-bisacrylamide starting aqueous solution, use Teflon stir Oar is stirred 8 minutes with 1100rpm speed.The starting aqueous solution is risen to 81 DEG C with 9 DEG C/min of speed and keeps being somebody's turn to do Temperature turns into gelatin gel until starting aqueous solution.The gel of formation is dried in the environment of low-temperature high-vacuum degree, should Gel is put into start in freeze drier sample disc and freezed by drying process using finished product freeze drier in the market Machine, treats that gelling temp is reduced to subzero 49 DEG C in sample disc, opens vavuum pump and improve vacuum, treats that gas pressure is reduced in system To below 30Pa, open baffle temperature control and start to dehydrate, other operating parameters take machine preset value, treat gas in system Pressure is stable dry and terminate after, be saturated concentration 80% by material immersion concentration after drying, the amount of ammonium fluoride material is water-soluble to originate Stirred in liquid in the ammonium fluoride aqueous solution of 8 times of the amount of bismuth nitrate material and in the case where Teflon stir oar is with 1120rpm speed Mix 25 seconds, filter thereafter, in 0.5% hydrogen and the gaseous mixture of 99.5% argon gas after being dried 5 hours in 100 DEG C of drying box 500 DEG C of constant temperature are warming up under body protection to cool down after 1.5 hours, prepare continuous conduction original position C/ metal solid solutions/Ni2+, Ca2+Adulterate BiF3Compound fluorination bismuth anode material for lithium-ion batteries.

Claims (1)

1. a kind of continuous conduction original position C/ metal solid solutions/Ni2+, Ca2+Adulterate BiF3Compound fluorination bismuth lithium ion cell positive material The preparation method of material, it is characterized in that:It is 5-15wt% bismuth nitrates, 0.1-0.5wt% nickel nitrates, 0.1-0.5wt% to prepare composition Calcium nitrate, 0.5-1wt% nitric acid, 6-12wt% acrylamides, 1-2wt%N, N '-methylene-bisacrylamide starting it is water-soluble The quality of liquid, wherein acrylamide is N, 6 times of N '-methylene-bisacrylamide quality, using Teflon stir oar with 900rpm-1200rpm speed is stirred 5-15 minutes;The starting aqueous solution is risen into 75-85 with 5-10 DEG C/min of speed DEG C and keep the temperature until starting aqueous solution turn into gelatin gel;The gel of formation is cold in finished product in the market Dried on lyophilizer, gel is put into freeze drier sample disc and starts refrigeration machine, treat that gelling temp is reduced in sample disc Subzero 50 DEG C to subzero 45-, open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 25-35Pa in system, open Baffle temperature control starts to dehydrate, and other operating parameters take machine preset value, treats that stable gas pressure drying terminates in system Afterwards, it is saturated concentration 70-90% by material immersion concentration after drying, the amount of ammonium fluoride material is bismuth nitrate thing in starting aqueous solution Stirred in the ammonium fluoride aqueous solution of 8-20 times of the amount of matter and in the case where Teflon stir oar is with 1000rpm-1200rpm speed 15-30 seconds, filter thereafter, mixing in 0.5% hydrogen and 99.5% argon gas after being dried 3-7 hour in 80-120 DEG C of drying box 450-550 DEG C of constant temperature is warming up under conjunction gas shield to cool down after 0.5-2 hours, prepares the C/ metal solid solutions of continuous conduction original position Body/Ni2+, Ca2+Adulterate BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
CN201710213006.0A 2017-03-25 2017-03-25 A kind of continuous conduction original position C/ metal solid solutions/Ni2+,Ca2+Adulterate BiF3Positive pole and preparation method Withdrawn CN106953083A (en)

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CN101071669A (en) * 2007-03-29 2007-11-14 上海大学 Method for preparing magnetic compound micro-sphere with core-shell structure by electron beam irradiation
CN101212050A (en) * 2007-12-21 2008-07-02 湘潭大学 Method for producing bismuth trifluoride anode material of Li secondary battery
CN102344151A (en) * 2011-06-23 2012-02-08 中山大学 Prussian blue nano-scale hollow olivary microballoons
CN104891570A (en) * 2015-04-19 2015-09-09 宁波大学 Liquid phase synthetic Zr<4+> doped bismuth fluoride lithium-ion battery positive electrode material and preparation method thereof

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Application publication date: 20170714