CN103682267B - A kind of carbon solid acid Aluminate doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material and preparation methods - Google Patents
A kind of carbon solid acid Aluminate doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material and preparation methods Download PDFInfo
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Abstract
Carbon solid acid Aluminate doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode material preparation methods are by the titanium phosphate lithium Li of sulfonation carbon solid acid, Aluminate and silicon, aluminium doping1.3Al0.1Ti1.9Si0.2P2.8O12With synthesis material in high energy ball mill through obtaining after ball milling heat treatment after a while. Sulfonation carbon solid acid, by iron ion coordination, forms complete electronic conduction link; Adopting the reactive group alkoxyl fast hydrolyzing of aluminate coupling agent is hydroxyl and lithium ion conducting agent Li1.3Al0.1Ti1.9Si0.2P2.8O12In 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 Li1.3Al0.1Ti1.9Si0.2P2.8O12Be combined in FeF3Particle surface, thus complete electronics and ionic conduction link formed, greatly improve FeF3The ionic conductivity of material and electronic conductivity, thus the chemical property of this material improved.
Description
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, circulation longevityLife is long, the high absolute advantage of power density, has at present to exceed 30,000,000,000 dollars of/year shares and to surpass in global portable power source market10% the speed crossed increases gradually. Particularly in recent years, along with petering out of fossil energy, solar energy, wind energy, biologyThe new forms of energy such as mass-energy become the alternative of traditional energy gradually, and wherein wind energy, solar energy have intermittence, continue for meetingSupply of electric power need to use a large amount of energy-storage batteries 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 provideLithium ion battery explosive growth point, also the performance of lithium ion battery is 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, the research and development of high power capacity positive electrodeCan alleviate that current lithium ion battery group volume is large, heavy weight, price high-leveled and difficult with meet high power consumption and high-power equipment needs inningsFace. But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time at 100-180mAh/gBetween, the low bottleneck that promotes lithium ion battery specific energy that become of positive electrode specific capacity. At present commercial lithium ion batteryFor practical widely positive electrode is LiCoO2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and actual specific capacity existsBetween 130-140mAh/g, and cobalt is strategic materials, expensive and have larger toxicity. Therefore countries in the world in recent years,Researcher be devoted to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, up till now, the lithium-ion electric filtering outPond positive pole reaches tens of kinds, but really has potential commercial applications prospect or appeared at positive electrode on market really veryLack. As lithium manganate having spinel structure LiMn2O4, its cost is lower, and than being easier to preparation, security performance is also relatively good, butCapacity is lower, and theoretical capacity is 148mAh/g, and actual capacity is at 100-120mAh/g, and this material capacity circulation keeps energyPower is not good, and under high temperature, capacity attenuation is very fast, Mn3+John-Teller effect and the dissolving in electrolyte perplexing and grinding for a long timeStudy carefully personnel. The LiNiO of layer structure2And LiMnO2Although have larger theoretical specific capacity, be respectively 275mAh/g and 285MAh/g, but their preparations are very difficult, poor heat stability, cyclicity is very poor, and capacity attenuation is very fast. And at present byWalk business-like LiFePO4 LiFePO4Cost is low, Heat stability is good, environmental friendliness, but its theoretical capacity approximately only has 170MAh/g, and actual capacity in about 140mAh/g [ChunSY, BlokingJT, ChiangYM, NatureMaterials,2002,1:123-128.]. There is at present the positive electrode that exceedes 200mAh/g specific capacity of market prospects to only have lithium vanadate Li1+xV3O8，Li1+xV3O8Material can have and has the capacity that even approaches 300mAh/g, but its electric discharge average voltage is lower and also production process in vanadiumOxide often toxicity is larger. High lithium is than on positive electrode in recent years, particularly manganese base manganese-nickel binary and manganese base manganese-nickel-cobalt ternaryThe high lithium of system solid solution is than positive electrode, have exceed the Capacity Ratio of 200mAh/g, higher heat endurance with respect to cheap becomingThis and receive people's concern, but performance under this material high magnification is very undesirable, limited its in electrokinetic cell shouldWith [Young-SikHong, YongJoonPark, etal., SolidStateIonics, 2005,176:1035-1042].
In recent years, FeF3Material is because its capacity is high, the low visual field that enters researcher of the prices of raw and semifnished materials. FeF3Material and biographyThe operation principle of system anode material for lithium-ion batteries is different, and traditional lithium ion cell positive and negative pole all exist the lithium ion canTo embed or the space of deintercalation, and lithium ion in electrolyte between positive pole and negative pole back and forth embedding and deintercalation and discharge as" rocking chair " battery that Armand etc. propose. And FeF3A kind of transition material, namely in whole discharge process,FeF3There is following variation [BadwayF, CosandeyF, PereiraN, etal., ElectrodesforLiBatteries, J.Electrochem.Soc.，2003,150(10)：A1318-A1327.]：
Li++FeF3+e→LiFeF3----(1)
LiFeF3+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 secondPortion is the displacement reaction of metal, and conversion has occurred parent lattice completely. The theoretical capacity of the first step is 237mAh.g-1; Completely anti-Should be able to realize the conversion of 3 electronics, the theoretical capacity of second stage is 474mAh.g-1; Total capacity is 711mAh.g-1; AlthoughThis material does not have clear and definite discharge platform, and average discharge volt is also lower, but it approaches 800mAh.g-1Theoretical specific capacity alsoIt is the attention that has obtained investigation of materials personnel height. But, pass through as Arai, Amatucci[BadwayF, PereiraN,CosandeyF, etal., J.Electrochem.Soc., 2003,150 (9): A1209-A1218.] etc. scholar's research find, be by itIt not is an easy thing that theoretical capacity major part discharges. First FeF3The non-constant of electronic conduction ability, simultaneously itsLithium ion conductivity is also very low, and product LiF after conversion is electronic body, and simultaneously the ability of conductive lithium ion is also very poor,Thereby cause FeF3The available capacity that material can utilize is lower, can only discharge in early days about 50-100mAh.g in research-1CanContrary capacity; Charging and discharging currents is little, and multiplying power property is poor; Polarization in charge and discharge process is comparatively serious, charging/discharging voltage platform gapVery large; Capacitance reserve ability is not good, and along with discharging and recharging the increase of number of times, capacity attenuation is serious. Afterwards Amatucci etc. by withMaterial with carbon element forms carbon/ferric flouride nano-complex (CMFNCs) through long-time high-energy ball milling and has improved its conductive capability, greatly carriesHigh its chemical property, its discharge capacity can reach 200mAh.g-1Left and right [BadwayF, MansourA.N, PereiraN,Etal., Chem.Mater., 2007,19 (17): 4129-4141.]. But, material with carbon element adhering to mainly on positive electrode particle surfaceBy physical absorption, complete carbonaceous conductive link is more difficult. Secondly, the capacity that this material is higher need to be in higher temperature(50-70 DEG C) just can discharge, and main cause is that the activation energy of conversion reaction of second stage is very high, needs higher temperature gramTake this activation energy and have reaction speed faster, the charging platform of this material and the voltage difference of discharge platform are very high in addition, are alsoReaction activity is high, the not good embodiment of reaction invertibity. Finally, because FeF3Material is slightly soluble in cold water, so conventionally adopt secondThe method preparation of alcohol 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 FeF3What the chemical property of positive electrode was primary is to seek a kind of electronic conductance that can simultaneously improve materialThe method of rate and lithium ion conductivity makes that preparation flow is simple as far as possible, cost is low, convenient and swift simultaneously, and this is to FeF3JustThe development and application of utmost point material is particularly important.
Summary of the invention
The present invention is directed to existing background technology and just proposing carbon solid acid Aluminate doping phosphoric acid titanium lithium three component surface modification ferric flouridesUtmost point material and preparation method. The method is by the titanium phosphate lithium Li of sulfonation carbon solid acid, Aluminate and silicon, aluminium doping1.3Al0.1Ti1.9Si0.2P2.8O12In high energy ball mill, after ball milling heat treatment after a while, obtain FeF with synthesis material3Positive electrode.Sulfonation carbon solid acid is by sulfonic group and FeF3Iron ion coordination, forms strong bonded, and sulfonation carbon solid acid is the good conductor of electronics,Contribute to form complete electrically conductive links; Li1.3Al0.1Ti1.9Si0.2P2.8O12The good conductor of lithium ion, in order to ensureLi1.3Al0.1Ti1.9Si0.2P2.8O12With FeF3Material close contact, forms complete lithium ion conducting link, adopts Aluminate couplingAgent, the reactive group of Aluminate is active strong, is hydroxyl and Li by alkoxyl fast hydrolyzing1.3Al0.1Ti1.9Si0.2P2.8O12In conjunction with alsoSulfonic group polycondensation on sulfonation carbon solid acid is simultaneously combined, electronic conductor sulfonation carbon solid acid and lithium ion conducting agentLi1.3Al0.1Ti1.9Si0.2P2.8O12Be combined in FeF3Particle surface, thus complete electronics and ionic conduction link formed, greatlyImprove FeF3The 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, it is characterized in that byAl2O3：SiO2：TiO2：NH4H2PO4：Li2CO3Evenly mix for the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio), add95% ethanol of 3%-9%, in ball mill with the rotating speed ball milling 10-50 hour of 100-500 rev/min, after ball milling finishes60 DEG C-80 DEG C, in the vacuum drying oven that pressure is 10Pa-100Pa, dry 2-10 hour, grinds in alms bowl and again grinds at agate after taking-up10-30 minute, the powder after grinding is warmed up to 600-1000 DEG C of insulation with the speed of 5-30 DEG C/min and makes for 5-16 hourLi1.3Al0.1Ti1.9Si0.2P2.8O12Solid electrolyte powder; 5-20g glucose is positioned in 90-120 DEG C of baking oven to dry 5-10 littleTime after in Muffle furnace constant temperature carbonization 5-10 hour at 700-900 DEG C of temperature, be positioned in crucible after cooling, add 10-15mLThe concentrated sulfuric acid obtains carbon solid acid after sulfonation 1-5 hour in 150-200 DEG C of baking oven; Will be containing crystallization water molysite and ammonium fluoride (mol ratioFor 1.0:3.0-3.6) with the percentage by weight Li that is 3-15%1.3Al0.1Ti1.9Si0.2P2.8O12Solid electrolyte powder, percentage by weightFor the carbon solid acid of 3-15%, auxiliary agent that percentage by weight is 0.5-3.0% and the percentage by weight Aluminate that is 0.5-3.0%,In high energy ball mill, under atmosphere protection, normal temperature ball milling, after 5-20 hour, takes out material, at the gaseous mixture of 5% hydrogen and 95% argon gasUnder body protection, be warmed up to 300-450 degree constant temperature cooling after 2-10 hour, prepare FeF3Positive electrode.
Above-mentioned is Fe (NO containing crystallization water molysite3)3·9H2O，FeCl3·6H2O and Fe2(SO4)3·9H2One in O;
Above-mentioned Aluminate is the one in distearyl acyl-oxygen aluminum isopropoxide acid esters, isopropyl two oleic acid acyloxy Aluminates.
Above-mentioned auxiliary agent is Tween-80, the one 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 FeF3Iron ion coordination, shapeBecome strong bonded, sulfonation carbon solid acid is the good conductor of electronics, contributes to form complete electrically conductive links; Li1.3Al0.1Ti1.9Si0.2P2.8O12The good conductor of lithium ion, in order to ensure Li1.3Al0.1Ti1.9Si0.2P2.8O12With FeF3Material close contact, shapeBecome complete lithium ion conducting link, adopt aluminate coupling agent, the reactive group of Aluminate is active strong, quick by alkoxylBe hydrolyzed to hydroxyl and Li1.3Al0.1Ti1.9Si0.2P2.8O12In conjunction with and the simultaneously sulfonic group polycondensation on sulfonation carbon solid acid be combined, electricElectronic conduction agent sulfonation carbon solid acid and lithium ion conducting agent Li1.3Al0.1Ti1.9Si0.2P2.8O12Be combined in FeF3Particle surface, thereby shapeBecome complete electronics and ionic conduction link, greatly improved FeF3The ionic conductivity of material and electronic conductivity, thus carryThe chemical property of high this material.
Brief description of the drawings
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.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: by Al2O3：SiO2：TiO2：NH4H2PO4：Li2CO3For the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio)Example is evenly mixed, and adds 3.5% 95% ethanol, in ball mill with the rotating speed ball milling of 110 revs/min 12 hours, ball milling knotIn the vacuum drying oven that is 15Pa at 65 DEG C of pressure after bundle, be dried 2.5 hours, after taking-up, grind in alms bowl and again grind 15 minutes at agate,Powder after grinding is warmed up to 650 DEG C of insulations with the speed of 6 DEG C/min and within 6 hours, makes Li1.3Al0.1Ti1.9Si0.2P2.8O12Solid-state electricitySeparate matter powder. 5g glucose is positioned over to constant temperature carbonization at 700 DEG C of temperature in Muffle furnace after dry 5 hours in 90 DEG C of baking ovens6 hours, be positioned in crucible after cooling, add the sulfonation in 150 DEG C of baking ovens of the 12mL concentrated sulfuric acid after 1 hour, to obtain carbon solid acid;By Fe (NO3)3·9H2The Li that O and ammonium fluoride (mol ratio is 1.0:3.1) and percentage by weight are 3.2%1.3Al0.1Ti1.9Si0.2P2.8O12The carbon solid acid that solid electrolyte powder, percentage by weight are 3%, Tween-80 and the percentage by weight that percentage by weight is 0.6%Be 0.6% distearyl acyl-oxygen aluminum isopropoxide acid esters in high energy ball mill under high-purity argon gas protection normal temperature ball milling after 5 hours, getGo out material, under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 300 degree constant temperature cooling after 2 hours, be prepared intoTo FeF3Positive electrode.
Embodiment 2: by Al2O3：SiO2：TiO2：NH4H2PO4：Li2CO3For the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio)Example is evenly mixed, and adds 8% 95% ethanol, and in ball mill, with the rotating speed ball milling of 450 revs/min 45 hours, ball milling finishedAfter in the vacuum drying oven that is 80Pa at 75 DEG C of pressure dry 8 hours, after taking-up, grind in alms bowl and again grind 25 minutes at agate, grindPowder after mill is warmed up to 900 DEG C of insulations with the speed of 25 DEG C/min and within 15 hours, makes Li1.3Al0.1Ti1.9Si0.2P2.8O12Solid-state electricitySeparate matter powder. After 20g glucose is positioned in 120 DEG C of baking ovens to dry 10 hours in Muffle furnace constant temperature carbon at 900 DEG C of temperatureChange 10 hours, be positioned in crucible after cooling, add the sulfonation in 190 DEG C of baking ovens of the 15mL concentrated sulfuric acid after 5 hours, to obtain carbon solidBody acid; By FeCl3·6H2The Li that O and ammonium fluoride (mol ratio is 1.0:3.6) and percentage by weight are 13%1.3Al0.1Ti1.9Si0.2P2.8O12The carbon solid acid that solid electrolyte powder, percentage by weight are 15%, span-60 and the weight percent that percentage by weight is 2.8%Than being 3.0% isopropyl two oleic acid acyloxy Aluminates normal temperature ball millings 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, prepareObtain FeF3Positive electrode.
Embodiment 3: by Al2O3：SiO2：TiO2：NH4H2PO4：Li2CO3For the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio)Example is evenly mixed, and adds 5% 95% ethanol, and in ball mill, with the rotating speed ball milling of 200 revs/min 25 hours, ball milling finishedAfter in the vacuum drying oven that is 60Pa at 70 DEG C of pressure dry 7 hours, after taking-up, grind in alms bowl and again grind 20 minutes at agate, grindPowder after mill is warmed up to 750 DEG C of insulations with the speed of 20 DEG C/min and within 12 hours, makes Li1.3Al0.1Ti1.9Si0.2P2.8O12Solid-state electricitySeparate matter powder. After 10g glucose is positioned in 100 DEG C of baking ovens to dry 7 hours in Muffle furnace constant temperature carbon at 800 DEG C of temperatureChange 7 hours, be positioned in crucible after cooling, add the sulfonation in 170 DEG C of baking ovens of the 12mL concentrated sulfuric acid after 3 hours, to obtain carbon solidBody acid; By Fe2(SO4)3·9H2The Li that O and ammonium fluoride (mol ratio is 1.0:3.5) and percentage by weight are 7%1.3Al0.1Ti1.9Si0.2P2.8O12The carbon solid acid that solid electrolyte powder, percentage by weight are 8%, the tx-10 that percentage by weight is 2.0% and heavyThe amount percentage isopropyl two oleic acid acyloxy Aluminates that are 2.1% normal temperature ball milling 15 under high-purity argon gas protection in high energy ball millAfter hour, take out material, under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 400 degree constant temperature cold after 8 hoursBut, prepare FeF3Positive electrode.
Embodiment 4: by Al2O3：SiO2：TiO2：NH4H2PO4：Li2CO3For the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio)Example is evenly mixed, and adds 4% 95% ethanol, and in ball mill, with the rotating speed ball milling of 400 revs/min 50 hours, ball milling finishedAfter in the vacuum drying oven that is 90Pa at 80 DEG C of pressure dry 5 hours, after taking-up, grind in alms bowl and again grind 20 minutes at agate, grindPowder after mill is warmed up to 600 DEG C of insulations with the speed of 25 DEG C/min and within 12 hours, makes Li1.3Al0.1Tii.9Si0.2P2.8O12Solid-state electricitySeparate matter powder. After 12g glucose is positioned in 100 DEG C of baking ovens to dry 7 hours in Muffle furnace constant temperature carbon at 850 DEG C of temperatureChange 8 hours, be positioned in crucible after cooling, add the sulfonation in 170 DEG C of baking ovens of the 12mL concentrated sulfuric acid after 3 hours, to obtain carbon solidBody acid; By Fe (NO3)3·9H2The Li that O and ammonium fluoride (mol ratio is 1.0:3.2) and percentage by weight are 10%1.3Al0.1Ti1.9 Si0.2P2.8O12The carbon solid acid that solid electrolyte powder, percentage by weight are 9%, the span-60 that percentage by weight is 2.5% andPercentage by weight is 1.0% isopropyl two oleic acid acyloxy Aluminates normal temperature ball millings under high pure nitrogen protection in high energy ball millAfter 10 hours, take out material, under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 300 degree constant temperature after 7 hoursCooling, prepare FeF3Positive electrode.
Embodiment 5: by Al2O3：SiO2：TiO2：NH4H2PO4：Li2CO3For the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio)Example is evenly mixed, and adds 5% 95% ethanol, and in ball mill, with the rotating speed ball milling of 250 revs/min 30 hours, ball milling finishedAfter in the vacuum drying oven that is 90Pa at 70 DEG C of pressure dry 8 hours, after taking-up, grind in alms bowl and again grind 10 minutes at agate, grindPowder after mill is warmed up to 700 DEG C of insulations with the speed of 5 DEG C/min and within 16 hours, makes Li1.3Al0.1Ti1.9Si0.2P2.8O12Solid-state electricitySeparate matter powder. After 6g glucose is positioned in 120 DEG C of baking ovens to dry 10 hours in Muffle furnace constant temperature carbon at 750 DEG C of temperatureChange 9 hours, be positioned in crucible after cooling, add the sulfonation in 180 DEG C of baking ovens of the 15mL concentrated sulfuric acid after 3 hours, to obtain carbon solidBody acid; By Fe2(SO4)3·9H2The Li that O and ammonium fluoride (mol ratio is 1.0:3.3) and percentage by weight are 12%1.3Al0.1Ti1.9Si0.2P2.8O12The carbon solid acid that solid electrolyte powder, percentage by weight are 3%, the span-60 that percentage by weight is 1.5% andPercentage by weight is 1.0% distearyl acyl-oxygen aluminum isopropoxide acid esters normal temperature ball milling under high pure nitrogen protection in high energy ball millAfter 15 hours, take out material, under 5% hydrogen and 95% argon gas mixed gas protected, be warmed up to 300 degree constant temperature after 8 hoursCooling, prepare FeF3Positive electrode.
Claims (5)
1. the preparation method of carbon solid acid Aluminate doping phosphoric acid titanium lithium three component surface modification ferric fluoride anode materials, is characterized in that for by Al2O3∶SiO2∶TiO2∶NH4H2PO4∶Li2CO3Taking mol ratio as 0.05: 0.2: 1.9: the ratio of 2.8: 0.65 is evenly mixed, add 95% ethanol of 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 DEG C-80 DEG C, pressure is dry 2-10 hour in the vacuum drying oven of 10Pa-100Pa, after taking-up, grind in alms bowl and again grind 10-30 minute at agate, the powder after grinding is warmed up to 600-1000 DEG C of insulation with the speed of 5-30 DEG C/min and within 5-16 hour, makes Li1.3Al0.1Ti1.9Si0.2P2.8O12Solid electrolyte powder; After 5-20g glucose is positioned in 90-120 DEG C of baking oven to dry 5-10 hour in Muffle furnace constant temperature carbonization 5-10 hour at 700-900 DEG C 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 DEG C of baking oven; Be 1.0 by mol ratio: the Li that is 3-15% containing crystallization water molysite and ammonium fluoride and percentage by weight of 3.0-3.61.3Al0.1Ti1.9Si0.2P2.8O12Aluminate that the carbon solid acid that solid electrolyte powder, percentage by weight are 3-15%, the auxiliary agent that percentage by weight is 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 FeF3Positive electrode.
2. preparation method according to claim 1, is characterized in that above-mentioned is Fe (NO containing crystallization water molysite3)3·9H2O，FeCl3·6H2O and Fe2(SO4)3·9H2One in O.
3. preparation method according to claim 1, is characterized in that above-mentioned Aluminate is the one in distearyl acyl-oxygen aluminum isopropoxide acid esters, isopropyl two oleic acid acyloxy Aluminates.
4. preparation method according to claim 1, is characterized in that above-mentioned auxiliary agent is Tween-80, the one in span-60 and tx-10.
5. preparation method according to claim 1, is characterized in that above-mentioned atmosphere is high pure nitrogen or high-purity argon gas.
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| CN114122316B (en) * | 2021-11-22 | 2024-01-30 | 远景动力技术(江苏)有限公司 | Negative electrode and use thereof |
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| CN103035899B (en) * | 2013-01-14 | 2015-05-27 | 山东天润丰新能源科技有限公司 | Method for performing carbon coating modification on nano-powder by adopting water-soluble polymer |
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