CN104916818B - A kind of liquid phase synthesis Al3+,Y3+Adulterate cubic structure fluorination bismuth anode material for lithium-ion batteries and preparation method thereof - Google Patents

A kind of liquid phase synthesis Al3+,Y3+Adulterate cubic structure fluorination bismuth anode material for lithium-ion batteries and preparation method thereof Download PDF

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CN104916818B
CN104916818B CN201510197216.6A CN201510197216A CN104916818B CN 104916818 B CN104916818 B CN 104916818B CN 201510197216 A CN201510197216 A CN 201510197216A CN 104916818 B CN104916818 B CN 104916818B
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aqueous solution
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bismuth
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lithium
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CN104916818A (en
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徐玲霞
水淼
徐晓萍
陈超
陈姝
舒杰
任元龙
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Jiaxing Yanzhi Network Technology Co ltd
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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
    • 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
    • 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

Abstract

A kind of liquid phase synthesis Al3+, Y3+Adulterated cubic structure fluorination bismuth anode material for lithium-ion batteries and preparation method thereof, and this method design by process conditions and is introduced a variety of auxiliary agents and prepare cubic structure fluorination bismuth by liquid phase reactor, and passes through Al3+, Y3+Doping improves the specific capacity and capacity holding capacity of material, and the fluorination bismuth material is used with more than 200mAh.g as anode material for lithium-ion batteries‑1Specific capacity.This method equipment requirement is low, and product purity is high, is avoided that in liquid phase reactor generation is fluorinated the side reaction products such as a variety of double salt of bismuth and with excellent chemical property.

Description

A kind of liquid phase synthesis Al3+,Y3+Adulterate cubic structure fluorination bismuth lithium ion cell positive material Material and preparation method thereof
Technical field
The present invention relates to a kind of electric positive electrode manufacture method technical field of high power capacity 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 in recent years Come, 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, screening Up to tens of kinds of the lithium ion cell positive gone out, but really have potential commercial applications prospect or be already present in the market just Pole material is really very few.Such as lithium manganate having spinel structure LiMn2O4, its cost is relatively low, is easier to prepare, security performance 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 capacity Circulate holding capacity it is not good, under high temperature capacity attenuation quickly, Mn3+John-Teller effects and dissolving in the electrolyte it is long Researcher has been annoying since phase.The LiNiO of layer structure2And LiMnO2Although there is larger theoretical specific capacity, it is respectively 275mAh/g and 285mAh/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 present4Cost is low, heat endurance is good, environment-friendly, but its theoretical capacity About there was only 170mAh/g, and actual capacity is in 140mAh/g or so [Chun SY, Bloking J T, Chiang Y M, Nature Materials, 2002,1：123-128.].The positive electrode more than 200mAh/g specific capacities for having market prospects at present only has vanadium Sour lithium Li1+xV3O8, Li1+xV3O8Material can have possesses even close to 300mAh/g capacity, but its discharge average voltage it is relatively low and And in production process barium oxide often toxicity is larger.High lithium is than on positive electrode in recent years, particularly manganese base manganese-nickel binary and The high lithium of manganese base manganese-nickel-cobalt ternary solid solution system is steady with the Capacity Ratio more than 200mAh/g, higher heat than positive electrode The cost of qualitative and relative moderate and paid close attention to by people, but the performance under the material high magnification is very undesirable, limitation Its application [Young-Sik Hong, Yong Joon Park, et al., Solid State in electrokinetic cell 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, Pereira N, 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 while also lacking warp because producing many costs height of waste liquid Ji property.Bismuth, which is fluorinated, as lithium ion secondary battery anode material also has a negative characteristic to be that its electronic conductivity is extremely low, Therefore very high polarizing voltage can be caused in charge and discharge process.
In addition fluorination bismuth crystal formation and pattern in lattice electrons transport property influence it is very big, therefore be directly connected to lithium from The chemical property of sub- battery such as charge/discharge rates, capacity and circulation volume holding capacity；Ion doping is a kind of effective tune The microstructure of lattice is saved, changes the means of lattice electron and ionic transport properties, however, ion doping even polyion is assisted Extremely complex to the mechanism of action of parent with doping, effect is often difficult to expect.
Therefore a kind of simple technique, product quality stabilization, the liquid phase synthesis fluorine with excellent electrochemical performance crystal formation are developed It is to be fluorinated the key that bismuth material is applied as secondary cell to change bismuth preparation method.
The content of the invention
The present invention proposes a kind of liquid phase synthesis Al for existing background technology3+, Y3+Adulterate cubic structure fluorination bismuth lithium from Sub- cell positive material and preparation method thereof, this method is by liquid phase reactor, and the design and introducing by process conditions are a variety of Auxiliary agent prepares cubic structure fluorination bismuth, and passes through Al3+, Y3+Doping improves the specific capacity and capacity holding capacity of material, should Fluorination bismuth material is used with more than 200mAh.g as anode material for lithium-ion batteries-1Specific capacity.This method equipment requirement Low, product purity is high, is avoided that in liquid phase reactor generation is fluorinated the side reaction products such as a variety of double salt of bismuth and with excellent Chemical property.
This liquid phase synthesis Al3+, Y3+Adulterate cubic structure fluorination bismuth method for preparing anode material of lithium-ion battery, and it is special Levy for：It is 5-15wt% bismuth nitrates, 0.1-0.5wt% aluminum nitrates, 0.1-0.5wt% yttrium nitrates, the dilute nitre of 1-5wt% to prepare composition Acid, 0.1-0.5wt% auxiliary agents Z1 water solution A 200-300mL；Prepare ammonium fluoride, 0.1- of the composition for 15-45wt% 0.5wt% auxiliary agents Z2 aqueous solution B 200-300mL；Water solution A is identical with aqueous solution B volume, ammonium fluoride in aqueous solution B Concentration is 3 times of nitric acid bi concns in water solution A；Prepare composition has for 0.1-0.5wt% auxiliary agent Z3,0.1-0.5wt% The auxiliary agent Z4 of cerium sulphate crystal effect aqueous solution C；Aqueous solution C is put into volume for 2L, internal diameter is anti-for 15-20 centimetres of cylinder Answer in device at the 1/3-1/2 of reactor cumulative volume, aqueous solution C temperature setting is used into polytetrafluoroethyl-ne simultaneously at 40-60 DEG C Alkene agitating paddle is stirred with 1200rpm-1500rpm speed.Using peristaltic pump at a same speed simultaneously by water solution A and water-soluble Liquid B is pumped into the ad-hoc location in reactor and until the whole pumps of the water solution A and aqueous solution B of all preparations are complete.By reactor Temperature is adjusted to 30-40 DEG C, maintains the speed of stirring constant, and reactor is placed in into the nitrogen that 1 atmospheric pressure volume ratio is 95: 5 Kept for 20-40 hours with hydrogen gas mixture.Thereafter, by filtering, 10-20 is dried in 100-150 DEG C of drying box small When after obtain Al3+, Y3+Adulterate cubic structure fluorination bismuth.
Auxiliary agent Z1 is one kind in monoethanolamine, triethanolamine, Triethanolammonium chloride in preparation method as described above；Auxiliary agent Z2 is polyvinylpyrrolidone of the mean molecule quantity between 20000-30000, and mean molecule quantity is in 10000-20000 polyethylene One kind in alcohol, op-10；Auxiliary agent Z3 is one kind in perfluoro-heptanoic acid, 2,2- difluoros cyclopropyl carboxylic acid, perfluoroglutaric acid；With knot The auxiliary agent Z4 of brilliant control action is one kind in following block copolymer：
(1) acrylic acid and the number-average molecular weight of NIPA block copolymer PAA-b-PNIPAM, PAA parts For 8000-12000, the number-average molecular weight of PNIPAM parts is 22000-26000, and molecular weight distributing index is 1.20-1.45；
(2) methacrylic acid and the number of methacrylic acid peopentyl ester block copolymer PMAA-b-PNPMA, PMAA parts are equal Molecular weight is 8000-12000, and the number-average molecular weight of PNPMA parts is 20000-24000, and molecular weight distributing index is 1.1- 1.3；
(3) acrylic acid and the number-average molecular weight of n-butyl acrylate block copolymer PnBuA-b-PAA, PnBuA parts are The number-average molecular weight of 7000-8000, PAA part is 5000-6000, and molecular weight distributing index is 1.4-1.6；
Three kinds of block copolymers as described above can directly be bought, such as Polymer Source companies of Canada.
The diameter of Teflon stir oar is smaller than the diameter of reactor 5 centimetres in preparation method as described above；Wriggle It is 0.1-1mL/ minutes that pump, which conveys water solution A and aqueous solution B speed,；Ad-hoc location as described above refers to water solution A and enters anti- The entrance and aqueous solution B for answering device enter the entrance of reactor in same plane and on using mixing paddle axle as the circle in the center of circle, and two The line of person is by the center of circle and diameter is smaller than the diameter of agitating paddle 1 centimetre.
Fig. 1 is charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of the material, voltage range 1.8V-4.0V, charging and discharging currents 0.1C.
Compared with prior art, the advantage of the invention is that：This method is by liquid phase reactor, and setting by process conditions Count and introduce a variety of auxiliary agents and prepare cubic structure fluorination bismuth, and pass through Al3+, Y3+Doping improves the specific capacity and appearance of material Holding capacity is measured, the fluorination bismuth material is used with more than 200mAh.g as anode material for lithium-ion batteries-1Specific capacity.Should Method equipment requirement is low, and product purity is high, is 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, 1wt% dust technologies, 0.1wt% aluminum nitrates, 0.1wt% to prepare 200mL compositions The water solution A of yttrium nitrate, 0.1wt% monoethanolamines；Prepare ammonium fluoride, 0.1wt% mean molecule quantity of the 200mL compositions for 15wt% The aqueous solution B of polyvinylpyrrolidone between 20000-30000；It is 0.1wt% perfluoro-heptanoic acids and 0.1wt% to prepare composition The aqueous solution C of acrylic acid and NIPA block copolymer PAA-b-PNIPAM；Aqueous solution C is put into 2L volumes, Internal diameter in 15 centimetres of cylindrical reactor at the 1/3 of reactor cumulative volume, aqueous solution C temperature setting is same at 40 DEG C When stirred using a diameter of 10 centimetres of Teflon stir oar with 1250rpm speed.Using peristaltic pump with 0.1mL/ points Water solution A and aqueous solution B are pumped into reactor and until the whole pumps of the water solution A and aqueous solution B of all preparations by clock rate degree simultaneously It is complete.Water solution A enters the entrance of reactor and aqueous solution B enters the entrance of reactor in same plane and positioned at mixing paddle axle For on the circle in the center of circle, both lines are by the center of circle and diameter is smaller than the diameter of agitating paddle 1 centimetre.At this moment by the temperature of reactor 30 DEG C are adjusted to, maintains the speed of stirring constant, reactor is placed in the nitrogen and hydrogen that an atmospheric pressure volume ratio is 95: 5 Kept for 20 hours in mixed gas.Thereafter, by filtering, Al is obtained after being dried 10 hours in 100 DEG C of drying box3+, Y3+Mix Miscellaneous cubic structure is fluorinated bismuth.
Embodiment 2：It is 15wt% bismuth nitrates, 0.5wt% aluminum nitrates, 0.4wt% yttrium nitrates, 5wt% to prepare 300mL compositions The water solution A of dust technology, 0.5wt% Triethanolammonium chlorides；Prepare 300mL compositions average for 45wt% ammonium fluoride, 0.5wt% Aqueous solution B of the molecular weight in 10000-20000 polyvinyl alcohol；Prepare composition be 0.5wt%2,2- difluoros cyclopropyl carboxylic acid and The aqueous solution C of 0.5wt% methacrylic acids and methacrylic acid peopentyl ester block copolymer PMAA-b-PNPMA；By aqueous solution C Be put into 2L volumes, internal diameter in 20 centimetres of cylindrical reactor at the 1/2 of reactor cumulative volume, by aqueous solution C temperature 60 DEG C are arranged on while being stirred using a diameter of 15 centimetres of Teflon stir oar with 1500rpm speed.Use wriggling Water solution A and aqueous solution B were pumped into reactor and until the water solution A of all preparations and water-soluble by pump simultaneously with 1mL/ minutes speed Liquid B whole pumps are complete.Water solution A enter entrance and the aqueous solution B of reactor into reactor entrance is in same plane and is located at On using mixing paddle axle as the circle in the center of circle, both lines are by the center of circle and diameter is smaller than the diameter of agitating paddle 1 centimetre.At this moment will be anti- Answer the temperature of device to be adjusted to 40 DEG C, maintain the speed of stirring constant, it is 95: 5 that reactor is placed in into an atmospheric pressure volume ratio Kept for 40 hours in nitrogen and hydrogen gas mixture.Thereafter, by filtering, obtained after being dried 20 hours in 150 DEG C of drying box Obtain Al3+, Y3+Adulterate cubic structure fluorination bismuth.
Embodiment 3：It is 10wt% bismuth nitrates, 0.3wt% aluminum nitrates, 0.3wt% yttrium nitrates, 3wt% to prepare 250mL compositions The water solution A of dust technology, 0.3wt% triethanolamines；It is 30wt% ammonium fluoride, 0.3wt%op-10 to prepare 250mL compositions Aqueous solution B；It is 0.3wt% perfluoroglutaric acids and 0.3wt% acrylic acid and n-butyl acrylate block copolymer to prepare composition PnBuA-b-PAA aqueous solution C；Aqueous solution C is put into 2L volumes, internal diameter in 17 centimetres of cylindrical reactor to reactor At the 2/5 of cumulative volume, by aqueous solution C temperature setting at 50 DEG C simultaneously using a diameter of 12 centimetres of Teflon stir oar Stirred with 1350rpm speed.Water solution A and aqueous solution B are pumped into by reaction with 0.5mL/ minutes speed simultaneously using peristaltic pump Device is simultaneously until the whole pumps of the water solution A and aqueous solution B of all preparations are complete.The entrance that water solution A enters reactor enters with aqueous solution B Enter the entrance of reactor in same plane and on using mixing paddle axle as the circle in the center of circle, both lines are by the center of circle and diameter It is smaller than the diameter of agitating paddle 1 centimetre.At this moment the temperature of reactor is adjusted to 35 DEG C, maintains the speed of stirring constant, will react Device is placed in the nitrogen and hydrogen gas mixture that an atmospheric pressure volume ratio is 95: 5 and kept for 30 hours.Thereafter, by filtering, Al is obtained after being dried 15 hours in 120 DEG C of drying box3+, Y3+Adulterate cubic structure fluorination bismuth.
Embodiment 4：It is 7wt% bismuth nitrates, 0.1wt% aluminum nitrates, 0.5wt% yttrium nitrates, 3wt% to prepare 250mL compositions The water solution A of dust technology, 0.3wt% Triethanolammonium chlorides；Prepare ammonium fluoride, 0.4wt%op- of the 250mL compositions for 21wt% 10 aqueous solution B；It is 0.4wt%2 to prepare composition, and 2- difluoros cyclopropyl carboxylic acid and 0.4wt% acrylic acid and n-butyl acrylate are embedding Section copolymer p nBuA-b-PAA aqueous solution C；Aqueous solution C is put into 2L volumes, internal diameter is in 18 centimetres of cylindrical reactor To the 2/5 of reactor cumulative volume, by aqueous solution C temperature setting at 40 DEG C simultaneously using a diameter of 13 centimetres of polytetrafluoroethyl-ne Alkene agitating paddle is stirred with 1200rpm speed.Using peristaltic pump with 0.5mL/ minutes speed simultaneously by water solution A and aqueous solution B It is pumped into reactor and until the whole pumps of the water solution A and aqueous solution B of all preparations is complete.Water solution A enter reactor entrance with Aqueous solution B enters the entrance of reactor in same plane and on using mixing paddle axle as the circle in the center of circle, and both lines pass through The center of circle and diameter is smaller than the diameter of agitating paddle 1 centimetre.At this moment the temperature of reactor is adjusted to 35 DEG C, maintains the speed of stirring not Become, reactor is placed in the nitrogen and hydrogen gas mixture that an atmospheric pressure volume ratio is 95: 5 and kept for 30 hours.Thereafter, pass through Filtering, Al is obtained after being dried 10 hours in 100 DEG C of drying box3+, Y3+Adulterate cubic structure fluorination bismuth.
Embodiment 5：It is 10wt% bismuth nitrates, 0.4wt% aluminum nitrates, 0.2wt% yttrium nitrates, 4wt% to prepare 290mL compositions The water solution A of dust technology, 0.3wt% triethanolamines；Prepare ammonium fluoride, 0.3wt% mean molecule of the 290mL compositions for 30wt% Measure the aqueous solution B of the polyvinylpyrrolidone between 20000-30000；Prepare composition for 0.3wt% perfluoroglutaric acids and The aqueous solution C of 0.2wt% methacrylic acids and methacrylic acid peopentyl ester block copolymer PMAA-b-PNPMA；By aqueous solution C Be put into 2L volumes, internal diameter in 20 centimetres of cylindrical reactor at the 2/5 of reactor cumulative volume, by aqueous solution C temperature 50 DEG C are arranged on while being stirred using a diameter of 15 centimetres of Teflon stir oar with 1350rpm speed.Use wriggling Water solution A and aqueous solution B were pumped into reactor and until the water solution A and water of all preparations by pump simultaneously with 0.5mL/ minutes speed Solution B whole pump is complete.Water solution A enters the entrance of reactor and aqueous solution B enters the entrance of reactor in same plane and position On using mixing paddle axle as the circle in the center of circle, both lines are by the center of circle and diameter is smaller than the diameter of agitating paddle 1 centimetre.At this moment will The temperature of reactor is adjusted to 35 DEG C, maintains the speed of stirring constant, and it is 95: 5 that reactor is placed in into an atmospheric pressure volume ratio Nitrogen and hydrogen gas mixture in keep 30 hours.Thereafter, by filtering, after being dried 15 hours in 120 DEG C of drying box Obtain Al3+, Y3+Adulterate cubic structure fluorination bismuth.

Claims (2)

1. a kind of liquid phase synthesis Al3+、Y3+The cubic structure that adulterates is fluorinated the preparation method of bismuth anode material for lithium-ion batteries, its feature It is that it is 5-15wt% bismuth nitrates, 0.1-0.5wt% aluminum nitrates, 0.1-0.5wt% yttrium nitrates, the dilute nitre of 1-5wt% to prepare composition Acid, 0.1-0.5wt% auxiliary agents Z1 water solution A 200-300mL；Prepare ammonium fluoride, 0.1- of the composition for 15-45wt% 0.5wt% auxiliary agents Z2 aqueous solution B 200-300mL；Water solution A is identical with aqueous solution B volume, ammonium fluoride in aqueous solution B Concentration is 3 times of nitric acid bi concns in water solution A；Prepare composition has for 0.1-0.5wt% auxiliary agent Z3,0.1-0.5wt% The auxiliary agent Z4 of cerium sulphate crystal effect aqueous solution C；Aqueous solution C is put into volume for 2L, internal diameter is anti-for 15-20 centimetres of cylinder Answer in device at the 1/3-1/2 of reactor cumulative volume, aqueous solution C temperature setting is used into polytetrafluoroethyl-ne simultaneously at 40-60 DEG C Alkene agitating paddle is stirred with 1200rpm-1500rpm speed；Using peristaltic pump at a same speed simultaneously by water solution A and water-soluble Liquid B is pumped into the ad-hoc location in reactor and until the whole pumps of the water solution A and aqueous solution B of all preparations are complete；By reactor Temperature is adjusted to 30-40 DEG C, maintains the speed of stirring constant, and reactor is placed in into the nitrogen that an atmospheric pressure volume ratio is 95: 5 Kept for 20-40 hours with hydrogen gas mixture；Thereafter, by filtering, 10-20 is dried in 100-150 DEG C of drying box small When after obtain Al3+、Y3+Adulterate cubic structure fluorination bismuth；
Auxiliary agent Z1 is one kind in monoethanolamine, triethanolamine, Triethanolammonium chloride in preparation method as described above；Auxiliary agent Z2 is Polyvinylpyrrolidone of the mean molecule quantity between 20000-30000, mean molecule quantity in 10000-20000 polyvinyl alcohol, One kind in op-10；Auxiliary agent Z3 is one kind in perfluoro-heptanoic acid, 2,2- difluoros cyclopropyl carboxylic acid, perfluoroglutaric acid；With crystallization control The auxiliary agent Z4 of making is one kind in following block copolymer：
(1) acrylic acid and the number-average molecular weight of NIPA block copolymer PAA-b-PNIPAM, PAA parts are The number-average molecular weight of 8000-12000, PNIPAM part is 22000-26000, and molecular weight distributing index is 1.20-1.45；
(2) methacrylic acid and the equal molecule of number of methacrylic acid peopentyl ester block copolymer PMAA-b-PNPMA, PMAA parts Measure as 8000-12000, the number-average molecular weight of PNPMA parts is 20000-24000, and molecular weight distributing index is 1.1-1.3；
(3) number-average molecular weight of acrylic acid and n-butyl acrylate block copolymer PnBuA-b-PAA, PnBuA parts is 7000- The number-average molecular weight of 8000, PAA parts is 5000-6000, and molecular weight distributing index is 1.4-1.6；
The diameter of Teflon stir oar is smaller than the diameter of reactor 5 centimetres in preparation method as described above；Peristaltic pump is defeated It is 0.1-1mL/ minutes to send water solution A and aqueous solution B speed；Ad-hoc location as described above refers to water solution A and enters reactor Entrance and aqueous solution B enter the entrance of reactor in same plane and on using mixing paddle axle as the circle in the center of circle, both Line is by the center of circle and diameter is smaller than the diameter of agitating paddle 1 centimetre.
2. Al according to claim 13+、Y3+The cubic structure that adulterates is fluorinated the preparation side of bismuth anode material for lithium-ion batteries Method, it is characterised in that the fluorination bismuth prepared has more than 200mAhg-1Specific capacity.
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CN102315482A (en) * 2011-08-31 2012-01-11 北京理工大学 Lithium secondary battery with metal fluoride as positive electrode material

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