CN103682267A - Carbon solid acid and aluminic acid ester doped ferric fluoride anode material with titanium-phosphate-lithium three-component surface modification, and preparation method of anode material - Google Patents

Carbon solid acid and aluminic acid ester doped ferric fluoride anode material with titanium-phosphate-lithium three-component surface modification, and preparation method of anode material Download PDF

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CN103682267A
CN103682267A CN201310456089.8A CN201310456089A CN103682267A CN 103682267 A CN103682267 A CN 103682267A CN 201310456089 A CN201310456089 A CN 201310456089A CN 103682267 A CN103682267 A CN 103682267A
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solid acid
carbon solid
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CN103682267B (en
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冯琳
水淼
徐晓萍
郑卫东
高珊
舒杰
任元龙
程亮亮
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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
    • 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
    • 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
    • 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
    • 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

The invention provides a preparation method of carbon solid acid and aluminic acid ester doped ferric fluoride anode material with titanium-phosphate-lithium three-component surface modification. The preparation method comprises the following steps: ball-milling sulfonated carbon solid acid, aluminic acid ester and titanium-phosphate-lithium doped with silicon and aluminum Li[1.3]A1[0.1]Ti[1.9]Si[0.2]P[2.8]O[12] and synthetic raw materials in a high-energy ball mill for a period of time and carrying out heat treatment. The preparation method is characterized in that sulfonated solid acid is coordinated through iron ions to form an integrated electron conduction link; reactive group alkoxy of an aluminic acid ester coupling reagent is adopted to rapidly hydrolyze into hydroxyl to be combined with the ionic conductive agent Li[1.3]A[10.1]Ti[1.9]Si[0.2]P[2.8]O[12] and combined with a sulfo group on the sulfonated carbon solid acid in a condensation manner at the same time, so as to combine the conductive agent sulfonated carbon solid acid and the ionic conductive agent Li[1.3]A[10.1]Ti[1.9]Si[0.2]P[2.8]O[12] on the surfaces of FeF3 particles, so that an electron and ionic conduction circuit is formed, the ionic conductivity and the electronic conductivity of the FeF3 material are improved greatly, and thus the electrochemical performance of the material is improved.

Description

A kind of carbon solid acid Aluminate doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material and preparation methods
Technical field
The present invention relates to a kind of high power capacity ferric flouride 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, have extended cycle life, the high absolute advantage of power density, in global portable power source market, have at present and surpass 30,000,000,000 dollars of/year shares and increase gradually to surpass 10% speed.Particularly in recent years, along with petering out of fossil energy, the new forms of energy such as solar energy, wind energy, biomass energy become the alternative of traditional energy gradually, and wherein wind energy, solar energy have intermittence, for meeting lasting supply of electric power needs, use a large amount of energy-storage batteries simultaneously; The urban air-quality problem that vehicle exhaust brings is day by day serious, and 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 the performance of lithium ion battery are had higher requirement simultaneously.
The raising of the capacity of anode material for lithium-ion batteries is the primary goal that scientific and technical personnel study, and the research and development of high power capacity positive electrode can alleviate that current lithium ion battery group volume is large, heavy weight, price are high-leveled and difficult to meet the situation of high power consumption and high-power equipment needs.Yet 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 that promotes lithium ion battery specific energy that become of positive electrode specific capacity.The current commercial lithium ion battery the most widely positive electrode of practicality is LiCoO 2, 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, the researcher of countries in the world is devoted to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, up till now, the lithium ion cell positive filtering out reaches tens of kinds, but really have potential commercial applications prospect or the positive electrode that appeared on market very few really.As lithium manganate having spinel structure LiMn 2o 4, its cost is lower, and than being easier to preparation, security performance is also relatively good, however capacity is lower, and theoretical capacity is 148mAh/g, and actual capacity is at 100-120mAh/g, and this material capacity circulation hold facility is not good, and under high temperature, capacity attenuation is very fast, Mn 3+john-Teller effect and the dissolving in electrolyte perplexing for a long time researcher.The LiNiO of layer structure 2and LiMnO 2although there is larger theoretical specific capacity, be respectively 275mAh/g and 285mAh/g, their preparations are very difficult, poor heat stability, cyclicity is very poor, and capacity attenuation is very fast.And business-like LiFePO4 LiFePO progressively at present 4cost is low, Heat stability is good, environmental friendliness, but its theoretical capacity approximately only has 170mAh/g, and actual capacity is in 140mAh/g left and right [Chun SY, Bloking J T, Chiang Y M, Nature Materials, 2002,1:123-128.].There is at present the positive electrode that surpasses 200mAh/g specific capacity of market prospects to only have lithium vanadate Li 1+xv 3o 8, Li 1+xv 3o 8material can have and has the capacity that even approaches 300mAh/g, but its electric discharge average voltage is lower and also production process in barium oxide often toxicity is larger.High lithium is than on positive electrode in recent years, particularly the high lithium of manganese base manganese-nickel binary and manganese base manganese-nickel-cobalt ternary solid solution system compares positive electrode, have surpass 200mAh/g Capacity Ratio, compared with high thermal stability, receive people's concern with relative cheap cost, yet the performance under this material high magnification is very undesirable, limited its application [Young-Sik Hong, Yong Joon Park in electrokinetic cell, et al., Solid State Ionics, 2005,176:1035-1042].
In recent years, FeF 3material is because its capacity is high, the low visual field that enters researcher of the prices of raw and semifnished materials.FeF 3the operation principle of material and traditional anode material for lithium-ion batteries is different, traditional lithium ion cell positive and negative pole all exist lithium ion to embed or the space of de-embedding, and lithium ion in electrolyte embeds back and forth between positive pole and negative pole and de-embedding and " rocking chair " battery of discharging and proposing as Armand etc.And FeF 3a kind of transition material, namely in whole discharge process, FeF 3there is following variation [Badway F, Cosandey F, Pereira N, et al., Electrodes for Li Batteries, J.Electrochem.Soc., 2003,150 (10): A1318-A1327.]:
Li ++FeF 3+e→LiFeF 3----(1)
LiFeF 3+2Li ++2e→3LiF+Fe-(2)
The first step and the namely lithium ion embedding of traditional lithium ion, in whole course of reaction, lattice does not have large variation; And second displacement reaction that is metal, there is conversion completely in parent lattice.The theoretical capacity of the first step is 237mAh.g -1; Complete reaction can realize the conversion of 3 electronics, and the theoretical capacity of second stage is 474mAh.g -1; Total capacity is 711mAh.g -1; Although this material does not have clear and definite discharge platform, average discharge volt is also lower, and it approaches 800mAh.g -1theoretical specific capacity still obtained the attention of investigation of materials personnel height.Yet, pass through as Arai Amatucci[Badway F, Pereira N, Cosandey F, et al., J.Electrochem.Soc., 2003,150 (9): A1209-A1218.] etc. scholar's research is found, its theoretical capacity major part be discharged not is an easy thing.First FeF 3the non-constant of electron conduction ability, simultaneously its lithium ion conductivity is also very low, and the product LiF after conversion is electronic body, the ability of conductive lithium ion is also very poor simultaneously, thereby has caused FeF 3the available capacity that material can utilize is lower, what study, can only discharge about 50-100mAh.g in early days -1reversible capacity; Charging and discharging currents is little, and multiplying power property is poor; Polarization in charge and discharge process is comparatively serious, and charging/discharging voltage platform has a long way to go; Capacitance reserve ability is not good, and along with discharging and recharging the increase of number of times, capacity attenuation is serious.Amatucci etc. had improved its conductive capability by forming carbon/ferric flouride nano-complex (CMFNCs) with material with carbon element through long-time high-energy ball milling afterwards, had greatly improved its chemical property, and its discharge capacity can reach 200mAh.g -1left and right [Badway F, Mansour A.N, Pereira N, et al., Chem.Mater., 2007,19 (17): 4129-4141.].But material with carbon element adhering on positive electrode particle surface mainly leaned on physical absorption, complete carbonaceous conductive link is more difficult.Secondly, the capacity that this material is higher need to just can discharge at higher temperature (50-70 ℃), main cause is that the activation energy of conversion reaction of second stage is very high, need to compared with high temperature, overcome this activation energy and there is reaction speed faster, the charging platform of this material and the voltage difference of discharge platform are very high in addition, also be that reaction activity is high, the not good embodiment of reaction invertibity.Finally, because FeF 3material is slightly soluble in cold water, so conventionally adopt the method preparation of ethanol liquid phase, needs to use a large amount of ethanol in building-up process, and economy is not good.Be unsuitable in industrial applications.
Therefore, improve FeF 3what the chemical property of positive electrode was primary is to seek a kind of method that can simultaneously improve electronic conductivity and the lithium ion conductivity of material, makes that preparation flow is simple as far as possible, cost is low, convenient and swift simultaneously, and this is to FeF 3the development and application of positive electrode is particularly important.
Summary of the invention
The present invention is directed to existing background technology and proposed carbon solid acid Aluminate doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material and preparation methods.The method is by the titanium phosphate lithium Li of sulfonation carbon solid acid, Aluminate and silicon, aluminium doping 1.3al 0.1ti 1.9si 0.2p 2.8o 12in high energy ball mill, after ball milling heat treatment after a while, obtain FeF with synthesis material 3positive electrode.Sulfonation carbon solid acid is by sulfonic group and FeF 3iron ion coordination, forms strong bonded, and sulfonation carbon solid acid is the good conductor of electronics, contributes to form complete electrically conductive links; Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12the good conductor of lithium ion, in order to guarantee Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12with FeF 3material close contact, forms complete lithium ion conducting link, adopts aluminate coupling agent, and the reactive group of Aluminate is active strong, by alkoxyl fast hydrolyzing, is hydroxyl and Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12in conjunction with and the simultaneously sulfonic group polycondensation on sulfonation carbon solid acid be combined, electronic conductor sulfonation carbon solid acid and lithium ion conducting agent Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12be combined in FeF 3particle surface, thus complete electronics and ionic conduction link formed, greatly improved FeF 3the ionic conductivity of material and electronic conductivity, thus the chemical property of this material improved.
Carbon solid acid Aluminate doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material preparation methods, is characterized in that Al 2o 3: SiO 2: TiO 2: NH 4h 2pO 4: Li 2cO 3for the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio) is evenly mixed, 95% ethanol that adds 3%-9%, in ball mill with the rotating speed ball milling 10-50 hour of 100-500 rev/min, after ball milling finishes at 60 ℃-80 ℃, pressure is dry 2-10 hour in the vacuum drying oven of 10Pa-100Pa, after taking-up, in agate grinds alms bowl, again grind 10-30 minute, the powder after grinding is warmed up to 600-1000 ℃ of insulation with the speed of 5-30 ℃/min and within 5-16 hour, makes Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12solid electrolyte powder; After 5-20g glucose is positioned in 90-120 ℃ of baking oven to dry 5-10 hour in Muffle furnace constant temperature carbonization 5-10 hour at 700-900 ℃ of temperature, after cooling, be positioned in crucible, add the 10-15mL concentrated sulfuric acid after sulfonation 1-5 hour, to obtain carbon solid acid in 150-200 ℃ of baking oven; The Li that will be 3-15% containing crystallization water molysite and ammonium fluoride (mol ratio is 1.0:3.0-3.6) and percentage by weight 1.3al 0.1ti 1.9si 0.2p 2.8o 12the Aluminate that the auxiliary agent that the carbon solid acid that solid electrolyte powder, percentage by weight are 3-15%, percentage by weight are 0.5-3.0% and percentage by weight are 0.5-3.0%, in high energy ball mill normal temperature ball milling after 5-20 hour under atmosphere protection; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 300-450 degree constant temperature cooling after 2-10 hour, prepare FeF 3positive electrode.
Above-mentioned is Fe (NO containing crystallization water molysite 3) 39H 2o, FeCl 36H 2o and Fe 2(SO 4) 39H 2a kind of in O;
Above-mentioned Aluminate is a kind of in distearyl acyl-oxygen aluminum isopropoxide acid esters, isopropyl two oleic acid acyloxy Aluminates.
Above-mentioned auxiliary agent is Tween-80, a kind of in span-60 and tx-10;
Above-mentioned atmosphere is high pure nitrogen or high-purity argon gas;
Fig. 1 is charging capacity, discharge capacity and the efficiency for charge-discharge figure of front 10 circulations of this material, voltage range 2.0V-4.0V, charging and discharging currents 0.1C.
Compared with prior art, the invention has the advantages that: sulfonation carbon solid acid is by sulfonic group and FeF 3iron ion coordination, forms strong bonded, and sulfonation carbon solid acid is the good conductor of electronics, contributes to form complete electrically conductive links; Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12the good conductor of lithium ion, in order to guarantee Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12with FeF 3material close contact, forms complete lithium ion conducting link, adopts aluminate coupling agent, and the reactive group of Aluminate is active strong, by alkoxyl fast hydrolyzing, is hydroxyl and Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12in conjunction with and the simultaneously sulfonic group polycondensation on sulfonation carbon solid acid be combined, electronic conductor sulfonation carbon solid acid and lithium ion conducting agent Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12be combined in FeF 3particle surface, thus complete electronics and ionic conduction link formed, greatly improved FeF 3the ionic conductivity of material and electronic conductivity, thus the chemical property of this material improved.
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 2.0V-4.0V, charging and discharging currents 0.1C.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: by Al 2o 3: SiO 2: TiO 2: NH 4h 2pO 4: Li 2cO 3for the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio) is evenly mixed, add 3.5% 95% ethanol, in ball mill with the rotating speed ball milling of 110 revs/min 12 hours, in the vacuum drying oven that is 15Pa at 65 ℃ of pressure after ball milling finishes, be dried 2.5 hours, after taking-up, in agate grinds alms bowl, again grind 15 minutes, the powder after grinding is warmed up to 650 ℃ of insulations with the speed of 6 ℃/min and within 6 hours, makes Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12solid electrolyte powder.Constant temperature carbonization 6 hours at 700 ℃ of temperature in Muffle furnace after 5g glucose is positioned in 90 ℃ of baking ovens to dry 5 hours, is positioned in crucible after cooling, adds the sulfonation in 150 ℃ of baking ovens of the 12mL concentrated sulfuric acid after 1 hour, to obtain carbon solid acid; By Fe (NO 3) 39H 2the Li that O and ammonium fluoride (mol ratio is 1.0:3.1) and percentage by weight are 3.2% 1.3al 0.1ti 1.9si 0.2p 2.8o 12the distearyl acyl-oxygen aluminum isopropoxide acid esters that the Tween-80 that the carbon solid acid that solid electrolyte powder, percentage by weight are 3%, percentage by weight are 0.6% and percentage by weight are 0.6% normal temperature ball milling after 5 hours under high-purity argon gas protection in high energy ball mill; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 300 degree constant temperature cooling after 2 hours, prepare FeF 3positive electrode.
Embodiment 2: by Al 2o 3: SiO 2: TiO 2: NH 4h 2pO 4: Li 2cO 3for the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio) is evenly mixed, add 8% 95% ethanol, in ball mill with the rotating speed ball milling of 450 revs/min 45 hours, in the vacuum drying oven that is 80Pa at 75 ℃ of pressure after ball milling finishes, be dried 8 hours, after taking-up, in agate grinds alms bowl, again grind 25 minutes, the powder after grinding is warmed up to 900 ℃ of insulations with the speed of 25 ℃/min and within 15 hours, makes Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12solid electrolyte powder.Constant temperature carbonization 10 hours at 900 ℃ of temperature in Muffle furnace after 20g glucose is positioned in 120 ℃ of baking ovens to dry 10 hours, is positioned in crucible after cooling, adds the sulfonation in 190 ℃ of baking ovens of the 15mL concentrated sulfuric acid after 5 hours, to obtain carbon solid acid; By FeCl 36H 2the Li that O and ammonium fluoride (mol ratio is 1.0:3.6) and percentage by weight are 13% 1.3al 0.1ti 1.9si 0.2p 2.8o 12the isopropyl two oleic acid acyloxy Aluminates that the span-60 that the carbon solid acid that solid electrolyte powder, percentage by weight are 15%, percentage by weight are 2.8% and percentage by weight are 3.0% normal temperature ball milling after 20 hours under high-purity argon gas protection in high energy ball mill; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 450 degree constant temperature cooling after 9 hours, prepare FeF 3positive electrode.
Embodiment 3: by Al 2o 3: SiO 2: TiO 2: NH 4h 2pO 4: Li 2cO 3for the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio) is evenly mixed, add 5% 95% ethanol, in ball mill with the rotating speed ball milling of 200 revs/min 25 hours, in the vacuum drying oven that is 60Pa at 70 ℃ of pressure after ball milling finishes, be dried 7 hours, after taking-up, in agate grinds alms bowl, again grind 20 minutes, the powder after grinding is warmed up to 750 ℃ of insulations with the speed of 20 ℃/min and within 12 hours, makes Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12solid electrolyte powder.Constant temperature carbonization 7 hours at 800 ℃ of temperature in Muffle furnace after 10g glucose is positioned in 100 ℃ of baking ovens to dry 7 hours, is positioned in crucible after cooling, adds the sulfonation in 170 ℃ of baking ovens of the 12mL concentrated sulfuric acid after 3 hours, to obtain carbon solid acid; By Fe 2(SO 4) 39H 2the Li that O and ammonium fluoride (mol ratio is 1.0:3.5) and percentage by weight are 7% 1.3al 0.1ti 1.9si 0.2p 2.8o 12the isopropyl two oleic acid acyloxy Aluminates that the tx-10 that the carbon solid acid that solid electrolyte powder, percentage by weight are 8%, percentage by weight are 2.0% and percentage by weight are 2.1% normal temperature ball milling after 15 hours under high-purity argon gas protection in high energy ball mill; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 400 degree constant temperature cooling after 8 hours, prepare FeF 3positive electrode.
Embodiment 4: by Al 2o 3: SiO 2: TiO 2: NH 4h 2pO 4: Li 2cO 3for the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio) is evenly mixed, add 4% 95% ethanol, in ball mill with the rotating speed ball milling of 400 revs/min 50 hours, in the vacuum drying oven that is 90Pa at 80 ℃ of pressure after ball milling finishes, be dried 5 hours, after taking-up, in agate grinds alms bowl, again grind 20 minutes, the powder after grinding is warmed up to 600 ℃ of insulations with the speed of 25 ℃/min and within 12 hours, makes Li 1.3al 0.1ti i.9si 0.2p 2.8o 12solid electrolyte powder.Constant temperature carbonization 8 hours at 850 ℃ of temperature in Muffle furnace after 12g glucose is positioned in 100 ℃ of baking ovens to dry 7 hours, is positioned in crucible after cooling, adds the sulfonation in 170 ℃ of baking ovens of the 12mL concentrated sulfuric acid after 3 hours, to obtain carbon solid acid; By Fe (NO 3) 39H 2the Li that O and ammonium fluoride (mol ratio is 1.0:3.2) and percentage by weight are 10% 1.3al 0.1ti 1.9si 0.2p 2.8o 12the isopropyl two oleic acid acyloxy Aluminates that the span-60 that the carbon solid acid that solid electrolyte powder, percentage by weight are 9%, percentage by weight are 2.5% and percentage by weight are 1.0% normal temperature ball milling after 10 hours under high pure nitrogen protection in high energy ball mill; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 300 degree constant temperature cooling after 7 hours, prepare FeF 3positive electrode.
Embodiment 5: by Al 2o 3: SiO 2: TiO 2: NH 4h 2pO 4: Li 2cO 3for the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio) is evenly mixed, add 5% 95% ethanol, in ball mill with the rotating speed ball milling of 250 revs/min 30 hours, in the vacuum drying oven that is 90Pa at 70 ℃ of pressure after ball milling finishes, be dried 8 hours, after taking-up, in agate grinds alms bowl, again grind 10 minutes, the powder after grinding is warmed up to 700 ℃ of insulations with the speed of 5 ℃/min and within 16 hours, makes Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12solid electrolyte powder.Constant temperature carbonization 9 hours at 750 ℃ of temperature in Muffle furnace after 6g glucose is positioned in 120 ℃ of baking ovens to dry 10 hours, is positioned in crucible after cooling, adds the sulfonation in 180 ℃ of baking ovens of the 15mL concentrated sulfuric acid after 3 hours, to obtain carbon solid acid; By Fe 2(SO 4) 39H 2the Li that O and ammonium fluoride (mol ratio is 1.0:3.3) and percentage by weight are 12% 1.3al 0.1ti 1.9si 0.2p 2.8o 12the distearyl acyl-oxygen aluminum isopropoxide acid esters that the span-60 that the carbon solid acid that solid electrolyte powder, percentage by weight are 3%, percentage by weight are 1.5% and percentage by weight are 1.0% normal temperature ball milling after 15 hours under high pure nitrogen protection in high energy ball mill; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 300 degree constant temperature cooling after 8 hours, prepare FeF 3positive electrode.

Claims (5)

1. carbon solid acid Aluminate doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material and preparation methods, is characterized in that Al 2o 3: SiO 2: TiO 2: NH 4h 2pO 4: Li 2cO 3for the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio) is evenly mixed, 95% ethanol that adds 3%-9%, in ball mill with the rotating speed ball milling 10-50 hour of 100-500 rev/min, after ball milling finishes at 60 ℃-80 ℃, pressure is dry 2-10 hour in the vacuum drying oven of 10Pa-100Pa, after taking-up, in agate grinds alms bowl, again grind 10-30 minute, the powder after grinding is warmed up to 600-1000 ℃ of insulation with the speed of 5-30 ℃/min and within 5-16 hour, makes Li 1.3al 0.1ti 1.9si 0.2p 2.8o 12solid electrolyte powder; After 5-20g glucose is positioned in 90-120 ℃ of baking oven to dry 5-10 hour in Muffle furnace constant temperature carbonization 5-10 hour at 700-900 ℃ of temperature, after cooling, be positioned in crucible, add the 10-15mL concentrated sulfuric acid after sulfonation 1-5 hour, to obtain carbon solid acid in 150-200 ℃ of baking oven; The Li that will be 3-15% containing crystallization water molysite and ammonium fluoride (mol ratio is 1.0:3.0-3.6) and percentage by weight 1.3al 0.1ti 1.9si 0.2p 2.8o 12the Aluminate that the auxiliary agent that the carbon solid acid that solid electrolyte powder, percentage by weight are 3-15%, percentage by weight are 0.5-3.0% and percentage by weight are 0.5-3.0%, in high energy ball mill normal temperature ball milling after 5-20 hour under atmosphere protection; take out material; under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 300-450 degree constant temperature cooling after 2-10 hour, prepare FeF 3positive electrode.
2. method according to claim 1, is characterized in that above-mentioned is Fe (NO containing crystallization water molysite 3) 39H 2o, FeCl 36H 2o and Fe 2(SO 4) 39H 2a kind of in O.
3. method according to claim 1, is characterized in that above-mentioned Aluminate is a kind of in distearyl acyl-oxygen aluminum isopropoxide acid esters, isopropyl two oleic acid acyloxy Aluminates.
4. method according to claim 1, is characterized in that above-mentioned auxiliary agent is Tween-80, a kind of in span-60 and tx-10.
5. method according to claim 1, is characterized in that above-mentioned atmosphere is high pure nitrogen or high-purity argon gas.
CN201310456089.8A 2013-09-18 2013-09-18 A kind of carbon solid acid Aluminate doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material and preparation methods Expired - Fee Related CN103682267B (en)

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