CN105914350A - Fe2O3/FeF3-2xOx/Fe<3+>,Ce<4+> doped zirconium fluoride layer structure positive electrode material of lithium battery and preparation method thereof - Google Patents
Fe2O3/FeF3-2xOx/Fe<3+>,Ce<4+> doped zirconium fluoride layer structure positive electrode material of lithium battery and preparation method thereof Download PDFInfo
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Abstract
The invention provides a Fe2O3/FeF3-2xOx/Fe<3+>,Ce<4+> doped zirconium fluoride layer structure positive electrode material of a lithium battery and a preparation method thereof. According to the method, Fe<3+>,Ce<4+> doped zirconium fluoride is prepared through solid-phase synthesis; then on the basis of the characteristic that FeF3 is prone to gradual oxidation into Fe2O3 at a high temperature, FeF3-2xOx (wherein 0<x<0.3) and a Fe2O3 layer successively coat Fe<3+>,Ce<4+> doped zirconium fluoride particles so as to improve surface electron conduction capability of Fe<3+>,Ce<4+> doped zirconium fluoride and to resist harmful effect of an organic electrolyte on particle surfaces; and comprehensive electrochemical performance of zirconium fluoride is greatly improved through Fe<3+>,Ce<4+> doping.
Description
Technical field
The present invention relates to a kind of high-performance Zirconium tetrafluoride. complex lithium electricity positive electrode manufacture method technical field.
Background technology
Lithium rechargeable battery have volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, have extended cycle life, the high absolute advantage of power density, at present the whole world portable power source market have more than 30,000,000,000 dollar/year shares and gradually increase with the speed more than 10%.The most in recent years, along with petering out of fossil energy, the new forms of energy such as solar energy, wind energy, biomass energy are increasingly becoming the alternative of traditional energy, and wherein wind energy, solar energy have intermittence, use substantial amounts of energy-storage battery for meeting lasting supply of electric power needs 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 have higher requirement the performance of lithium ion battery simultaneously.
The raising of the capacity of anode material for lithium-ion batteries is the primary goal that scientific and technical personnel study, and the research and development of high power capacity positive electrode can alleviate that current Li-ion batteries piles volume is big, heavy weight, price are high-leveled and difficult to meet high power consumption and the situation of high-power equipment needs.But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time between 100-180mAh/g, positive electrode specific capacity is low has become as the bottleneck promoting lithium ion battery specific energy.The positive electrode of the most commercial most commonly used practicality of lithium ion battery is 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 bigger toxicity.The most in recent years, the research worker 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 most tens of kinds of the lithium ion cell positive filtered out, but really have potential commercial applications prospect or the positive electrode that is already present on market the fewest.Such as lithium manganate having spinel structure LiMn2O4, its cost is relatively low, is easier preparation, and security performance is relatively good, but capacity is relatively low, and theoretical capacity is 148mAh/g, and actual capacity is at 100-120mAh/g, and this material capacity circulation holding capacity is the best, and under high temperature, capacity attenuation is quickly, Mn3+John-Teller effect and dissolving in the electrolyte annoying research worker for a long time.The LiNiO of layer structure2And LiMnO2Although having bigger theoretical specific capacity, respectively 275mAh/g and 285mAh/g, but they preparing extremely difficult, poor heat stability, cyclicity is very poor, and capacity attenuation is quickly.And current the most business-like LiFePO4 LiFePO4Low cost, Heat stability is good, environmental friendliness, but its theoretical capacity about only has 170mAh/g, and actual capacity is at about 140mAh/g [Chun SY, Bloking J T, Chiang Y M, Nature Materials, 2002,1:123-128.].The positive electrode more than 200mAh/g specific capacity having market prospect at present only has lithium vanadate Li1+xV3O8, Li1+xV3O8Material can have and has even close to the capacity of 300mAh/g, but its electric discharge average voltage relatively low and in production process barium oxide often toxicity bigger.The highest lithium ratio is on positive electrode, the particularly high lithium of manganio manganese-nickel binary and manganio manganese-nickel-cobalt ternary solid solution system compares positive electrode, there is the Capacity Ratio more than 200mAh/g, higher heat stability and the cost of relative moderate and paid close attention to by people, but performance under this material high magnification is the most undesirable, limit its application [Young-Sik Hong in electrokinetic cell, Yong Joon Park, et al., Solid State Ionics, 2005,176:1035-1042].
In recent years, fluoride positive electrode is owing to its capacity is high, the prices of raw materials are low and enter the visual field of researcher.Fluoride materials is different with the operation principle of conventional lithium ion battery positive electrode, all there is lithium ion and can embed or the space of deintercalation in traditional lithium ion cell positive and negative pole, and " rocking chair " battery that the lithium ion in electrolyte embeds the most back and forth and deintercalation and discharging is proposed as Armand etc..Fluoride is then a kind of transition material, namely in whole discharge process, although Me has nothing in common with each other, MeFnSimilar following change [Badway F, CosandeyF, Pereira N, et al., Electrodes for Li Batteries, J.Electrochem.Soc., 2003,150 (10): A1318-A1327.] can occur:
nLi++MeFn+ne-→nLiF+Me0
Can discharge more than 200mAh.g in this process-1Specific capacity, thus obtain investigation of materials personnel height attention.In fluoride, the metal ion valence state of variable valence is the highest, then the capacity of this material is it is possible to the biggest, and in Zirconium tetrafluoride., zirconium valence state is+4 valencys, because having higher capacity than the fluoride of trivalent such as ferric flouride.But at present Zirconium tetrafluoride. lithium electricity positive electrode is due to preparation difficulty, the stability factor such as not in organic electrolyte, relevant research and development are the most considerably less.Additionally Zirconium tetrafluoride. also has a negative characteristic to be i.e. that its electronic conductivity is extremely low as lithium ion secondary battery anode material, therefore can cause the highest polarizing voltage in charge and discharge process.Generally ion doping and surface coating modification are effectively to regulate surface microstructure, change material electronics and the means of ionic transport properties, it is possible to improve the chemical property of material.But battery material is after experience repeatedly circulation, covering material is caused to lose efficacy from the disengaging of fertile material due to change in volume in cyclic process of the lattice mismatch of covering material and fertile material and fertile material.
Therefore develop that a kind of technique is simple, constant product quality, the modified fluorinated zirconium preparation method with excellent electrochemical performance are the keys that Zirconium tetrafluoride. material is applied as secondary cell.
Summary of the invention
The present invention is directed to existing background technology and propose a kind of Fe2O3|FeF3-2xOx|Fe3+, Ce4+Doping fluorination zirconium layer structure lithium electricity positive electrode and preparation method, the method uses solid phase synthesis Fe3+, Ce4+After doping Zirconium tetrafluoride., according to FeF3Easily progressively it is oxidized into Fe at relatively high temperatures2O3Characteristic, at Fe3+, Ce4+FeF it is coated with successively outside doping Zirconium tetrafluoride. granule3-2xOx, 0 ＜ x ＜ 0.3, and Fe2O3Layer is to improve Fe3+, Ce4+The doping surface electronic conductive capability of Zirconium tetrafluoride. and resist the organic electrolyte illeffects to material granule surface；In clad, the content of oxygen changes gradually, forms gradient-structure, additionally mixed with Fe in Zirconium tetrafluoride. lattice3+, also can improve mating of clad and bulk lattice, thus the clad significantly improving material change in volume in cyclic process and causing comes off；Pass through Ce simultaneously4+Doping changes the level structure of material, reduces ion migration activation energy, thus increases substantially the comprehensive electrochemical of Zirconium tetrafluoride..
This Fe2O3|FeF3-2xOx|Fe3+, Ce4+Doping fluorination zirconium layer structure lithium electricity method for preparing anode material, it is characterized by: by zirconates, the ammonium fluoride of amount 4.0-4.5 times of zirconates material, the amount 0.5-5% cerium salt of zirconates material, the amount 0.5-5% iron salt of zirconates material, the glycerol of zirconates quality 0.5-5% and ethylene glycol put into ball mill with after mixing liquid mixing that volume ratio is 1: 1, ball milling is 20: 1 with the mass ratio of material, with speed ball milling 10-20 hour of 200-400 rev/min, material is taken out after ball milling, after three times are washed, Fe is prepared after being dried 10-20 hour in 100 DEG C of-120 DEG C of drying baker3+, Ce4+Doping Zirconium tetrafluoride.；It is iron salt and the Fe of ammonium fluoride gross mass 80-170 times by the iron salt that amount ratio is 1: 3.0-3.6 and ammonium fluoride, the quality of material3+, Ce4+Doping Zirconium tetrafluoride., iron salt and the quaternary ammonium salt with fluorine as anion of 2-10% of ammonium fluoride gross mass, quality as iron salt, ammonium fluoride and Fe3+, Ce4+Putting into ball mill after the dehydrated alcohol mixing of doping Zirconium tetrafluoride. gross mass 0.5-4%, ball milling is 20: 1 with the mass ratio of material, takes out material with the speed ball milling of 300-500 rev/min after 10-20 hour；Putting in tube furnace by this material, being passed through flow is 1-10L h-1The oxygen that volume ratio is 10: 90 and argon mixed gas, with the speed of 2-10 DEG C/min be warmed up to 180-260 DEG C and at this temperature keep 15-36 minute；I.e. put into an air atmosphere after being taken out by this material, temperature constant is to keep the 10-30 second in the Muffle furnace of 800 DEG C, then takes out and is cooled to room temperature under room temperature in argon gas atmosphere and prepares Fe2O3|FeF3-2xOx|Fe3+, Ce4+Doping fluorination zirconium layer structure lithium electricity positive electrode.
Zirconates in preparation method as above is Zr (NO3)4·5H2O, ZrO (NO3)2·2H2One in O；Cerium salt is Ce (NH4)2(NO3)6、Ce(SO4)2·4H2One in O；Iron salt is the one in Fe(NO3)39H2O, Iron(III) chloride hexahydrate；Quaternary ammonium salt with fluorine as anion is tetra-n-butyl ammonium fluoride, one in Methanaminium, N,N,N-trimethyl-, fluoride, benzyl trimethyl ammonium fluoride.
Fig. 1 is charging capacity, discharge capacity and the efficiency for charge-discharge figure of front 10 circulations of this material, voltage range 1.8V-4.0V, charging and discharging currents 0.5C.
Compared with prior art, it is an advantage of the current invention that: use solid phase synthesis Fe3+, Ce4+Doping Zirconium tetrafluoride., at Fe3+, Ce4+FeF it is coated with successively outside doping Zirconium tetrafluoride. granule3-2xOx, 0 ＜ x ＜ 0.3, and Fe2O3Layer is to improve Fe3+, Ce4+The doping surface electronic conductive capability of Zirconium tetrafluoride. and resist the organic electrolyte illeffects to material granule surface；In clad, the content of oxygen changes gradually, forms gradient-structure, additionally mixed with Fe in Zirconium tetrafluoride. lattice3+, also can improve mating of clad and bulk lattice, thus the clad significantly improving material change in volume in cyclic process and causing comes off；Pass through Ce simultaneously4+Doping changes the level structure of material, reduces ion migration activation energy, thus increases substantially the comprehensive electrochemical of Zirconium tetrafluoride..
Accompanying drawing explanation
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of front 10 circulations of this material of Fig. 1, voltage range 1.8V-4.0V, charging and discharging currents 0.5C.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: by Zr (NO3)4·5H2O、Zr(NO3)4·5H2The ammonium fluoride of the amount of O material 4.0 times, Zr (NO3)4·5H2Amount 0.7%Ce (the NH of O material4)2(NO3)6、Zr(NO3)4·5H2Amount 0.7% Fe(NO3)39H2O of O material, Zr (NO3)4·5H2The glycerol of O mass 0.7% and ethylene glycol put into ball mill with after mixing liquid mixing that volume ratio is 1: 1, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 10 hours of 200 revs/min, material is taken out after ball milling, after three times are washed, after being dried 10 hours in 100 DEG C of drying baker, prepare Fe3+, Ce4+Doping Zirconium tetrafluoride.；It is Fe(NO3)39H2O and the Fe of ammonium fluoride gross mass 90 times by the Fe(NO3)39H2O that amount ratio is 1: 3.0 and ammonium fluoride, the quality of material3+, Ce4+The tetra-n-butyl ammonium fluoride of the 3% of doping Zirconium tetrafluoride., Fe(NO3)39H2O and ammonium fluoride gross mass, quality are Fe(NO3)39H2O, ammonium fluoride and Fe3+, Ce4+Putting into ball mill after the dehydrated alcohol mixing of doping Zirconium tetrafluoride. gross mass 0.7%, ball milling is 20: 1 with the mass ratio of material, takes out material with the speed ball millings of 350 revs/min after 12 hours；Putting in tube furnace by this material, being passed through flow is 2L h-1The oxygen that volume ratio is 10: 90 and argon mixed gas, with the speed of 2 DEG C/min be warmed up to 180 DEG C and at this temperature keep 15 minutes；I.e. put into an air atmosphere after being taken out by this material, temperature constant is to keep 10 seconds in the Muffle furnace of 800 DEG C, then takes out and is cooled to room temperature under room temperature in argon gas atmosphere and prepares Fe2O3|FeF3-2xOx|Fe3+, Ce4+Doping fluorination zirconium layer structure lithium electricity positive electrode.
Embodiment 2: by Zr (NO3)4·5H2O、Zr(NO3)4·5H2The ammonium fluoride of the amount of O material 4.2 times, Zr (NO3)4·5H2Amount 3%Ce (the NH of O material4)2(NO3)6、Zr(NO3)4·5H2Amount 3% Fe(NO3)39H2O of O material, Zr (NO3)4·5H2The glycerol of O mass 3% and ethylene glycol put into ball mill with after mixing liquid mixing that volume ratio is 1: 1, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 15 hours of 300 revs/min, material is taken out after ball milling, after three times are washed, after being dried 16 hours in 110 DEG C of drying baker, prepare Fe3+, Ce4+Doping Zirconium tetrafluoride.；It is Fe(NO3)39H2O and the Fe of ammonium fluoride gross mass 120 times by the Fe(NO3)39H2O that amount ratio is 1: 3.3 and ammonium fluoride, the quality of material3+, Ce4+The tetra-n-butyl ammonium fluoride of the 6% of doping Zirconium tetrafluoride., Fe(NO3)39H2O and ammonium fluoride gross mass, quality are Fe(NO3)39H2O, ammonium fluoride and Fe3+, Ce4+Putting into ball mill after the dehydrated alcohol mixing of doping Zirconium tetrafluoride. gross mass 2%, ball milling is 20: 1 with the mass ratio of material, takes out material with the speed ball millings of 350 revs/min after 15 hours；Putting in tube furnace by this material, being passed through flow is 5L h-1The oxygen that volume ratio is 10: 90 and argon mixed gas, with the speed of 6 DEG C/min be warmed up to 220 DEG C and at this temperature keep 25 minutes；I.e. put into an air atmosphere after being taken out by this material, temperature constant is to keep 15 seconds in the Muffle furnace of 800 DEG C, then takes out and is cooled to room temperature under room temperature in argon gas atmosphere and prepares Fe2O3|FeF3-2xOx|Fe3+, Ce4+Doping fluorination zirconium layer structure lithium electricity positive electrode.
Embodiment 3: by Zr (NO3)4·5H2O、Zr(NO3)4·5H2The ammonium fluoride of the amount of O material 4.5 times, Zr (NO3)4·5H2Amount 4.5%Ce (the NH of O material4)2(NO3)6、Zr(NO3)4·5H2Amount 4.5% Iron(III) chloride hexahydrate of O material, Zr (NO3)4·5H2The glycerol of O mass 4.5% and ethylene glycol put into ball mill with after mixing liquid mixing that volume ratio is 1: 1, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 20 hours of 400 revs/min, material is taken out after ball milling, after three times are washed, after being dried 20 hours in 120 DEG C of drying baker, prepare Fe3+, Ce4+Doping Zirconium tetrafluoride.；It is Iron(III) chloride hexahydrate and the Fe of ammonium fluoride gross mass 170 times by the Iron(III) chloride hexahydrate that amount ratio is 1: 3.6 and ammonium fluoride, the quality of material3+, Ce4+The Methanaminium, N,N,N-trimethyl-, fluoride of the 10% of doping Zirconium tetrafluoride., Iron(III) chloride hexahydrate and ammonium fluoride gross mass, quality are Iron(III) chloride hexahydrate, ammonium fluoride and Fe3+, Ce4+Putting into ball mill after the dehydrated alcohol mixing of doping Zirconium tetrafluoride. gross mass 3%, ball milling is 20: 1 with the mass ratio of material, takes out material with the speed ball millings of 450 revs/min after 20 hours；Putting in tube furnace by this material, being passed through flow is 9L h-1The oxygen that volume ratio is 10: 90 and argon mixed gas, with the speed of 9 DEG C/min be warmed up to 260 DEG C and at this temperature keep 30 minutes；I.e. put into an air atmosphere after being taken out by this material, temperature constant is to keep 30 seconds in the Muffle furnace of 800 DEG C, then takes out and is cooled to room temperature under room temperature in argon gas atmosphere and prepares Fe2O3|FeF3-2xOx|Fe3+, Ce4+Doping fluorination zirconium layer structure lithium electricity positive electrode.
Embodiment 4: by ZrO (NO3)2·2H2O、ZrO(NO3)2·2H2The ammonium fluoride of the amount of O material 4.2 times, ZrO (NO3)2·2H2Amount 4%Ce (the SO of O material4)2·4H2O、ZrO(NO3)2·2H2Amount 4% Iron(III) chloride hexahydrate of O material, ZrO (NO3)2·2H2The glycerol of O mass 4% and ethylene glycol put into ball mill with after mixing liquid mixing that volume ratio is 1: 1, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 20 hours of 400 revs/min, material is taken out after ball milling, after three times are washed, after being dried 15 hours in 120 DEG C of drying baker, prepare Fe3+, Ce4+Doping Zirconium tetrafluoride.；It is Iron(III) chloride hexahydrate and the Fe of ammonium fluoride gross mass 150 times by the Iron(III) chloride hexahydrate that amount ratio is 1: 3.5 and ammonium fluoride, the quality of material3+, Ce4+The Methanaminium, N,N,N-trimethyl-, fluoride of the 10% of doping Zirconium tetrafluoride., Iron(III) chloride hexahydrate and ammonium fluoride gross mass, quality are Iron(III) chloride hexahydrate, ammonium fluoride and Fe3+, Ce4+Putting into ball mill after the dehydrated alcohol mixing of doping Zirconium tetrafluoride. gross mass 2%, ball milling is 20: 1 with the mass ratio of material, takes out material with the speed ball millings of 400 revs/min after 20 hours；Putting in tube furnace by this material, being passed through flow is 7L h-1The oxygen that volume ratio is 10: 90 and argon mixed gas, with the speed of 8 DEG C/min be warmed up to 230 DEG C and at this temperature keep 25 minutes；I.e. put into an air atmosphere after being taken out by this material, temperature constant is to keep 20 seconds in the Muffle furnace of 800 DEG C, then takes out and is cooled to room temperature under room temperature in argon gas atmosphere and prepares Fe2O3|FeF3-2xOx|Fe3+, Ce4+Doping fluorination zirconium layer structure lithium electricity positive electrode.
Embodiment 5: by ZrO (NO3)2·2H2O、ZrO(NO3)2·2H2The ammonium fluoride of the amount of O material 4.0 times, ZrO (NO3)2·2H2Amount 0.5%Ce (the SO of O material4)2·4H2O、ZrO(NO3)2·2H2Amount 0.5% Iron(III) chloride hexahydrate of O material, ZrO (NO3)2·2H2The glycerol of O mass 0.5% and ethylene glycol put into ball mill with after mixing liquid mixing that volume ratio is 1: 1, ball milling is 20: 1 with the mass ratio of material, with the speed ball milling 10 hours of 400 revs/min, material is taken out after ball milling, after three times are washed, after being dried 13 hours in 100 DEG C of drying baker, prepare Fe3+, Ce4+Doping Zirconium tetrafluoride.；It is Iron(III) chloride hexahydrate and the Fe of ammonium fluoride gross mass 160 times by the Iron(III) chloride hexahydrate that amount ratio is 1: 3.5 and ammonium fluoride, the quality of material3+, Ce4+The benzyl trimethyl ammonium fluoride of the 7% of doping Zirconium tetrafluoride., Iron(III) chloride hexahydrate and ammonium fluoride gross mass, quality are Iron(III) chloride hexahydrate, ammonium fluoride and Fe3+, Ce4+Putting into ball mill after the dehydrated alcohol mixing of doping Zirconium tetrafluoride. gross mass 2%, ball milling is 20: 1 with the mass ratio of material, takes out material with the speed ball millings of 300 revs/min after 10 hours；Putting in tube furnace by this material, being passed through flow is 3L h-1The oxygen that volume ratio is 10: 90 and argon mixed gas, with the speed of 5 DEG C/min be warmed up to 210 DEG C and at this temperature keep 25 minutes；I.e. put into an air atmosphere after being taken out by this material, temperature constant is to keep 20 seconds in the Muffle furnace of 800 DEG C, then takes out and is cooled to room temperature under room temperature in argon gas atmosphere and prepares Fe2O3|FeF3-2xOx|Fe3+, Ce4+Doping fluorination zirconium layer structure lithium electricity positive electrode.
Claims (2)
1. a Fe2O3|FeF3-2xOx|Fe3+, Ce4+Doping fluorination zirconium layer structure lithium electricity positive electrode, it is characterised in that use solid phase synthesis
Fe3+, Ce4+After doping Zirconium tetrafluoride., at Fe3+, Ce4+FeF it is coated with successively outside doping Zirconium tetrafluoride. granule3-2xOx, 0 ＜ x ＜ 0.3, and Fe2O3
Layer, at FeF3-2xOx, in 0 ＜ x ＜ 0.3 clad, the content of oxygen changes gradually, forms gradient-structure；Preparation process is: by zirconium
Salt, the ammonium fluoride of amount 4.0-4.5 times of zirconates material, the amount 0.5-5% cerium salt of zirconates material, the amount 0.5-5% ferrum of zirconates material
Salt, the glycerol of zirconates quality 0.5-5% and ethylene glycol put into ball mill, ball milling with after mixing liquid mixing that volume ratio is 1: 1
Son and the mass ratio of material are 20: 1, with speed ball milling 10-20 hour of 200-400 rev/min, take out material after ball milling,
After three times are washed, after being dried 10-20 hour in 100 DEG C of-120 DEG C of drying baker, prepare Fe3+, Ce4+Doping Zirconium tetrafluoride.；Will
The iron salt that amount ratio is 1: 3.0-3.6 of material and ammonium fluoride, quality are iron salt and the Fe of ammonium fluoride gross mass 80-170 times3+, Ce4+
Doping Zirconium tetrafluoride., iron salt and the quaternary ammonium salt with fluorine as anion of 2-10% of ammonium fluoride gross mass, quality as iron salt, ammonium fluoride
And Fe3+, Ce4+Ball mill, ball milling and the mass ratio of material is put into after the dehydrated alcohol mixing of doping Zirconium tetrafluoride. gross mass 0.5-4%
It is 20: 1, to take out material after speed ball milling 10-20 hour of 300-500 rev/min；This material is put in tube furnace, logical
Inbound traffics are 1-10L h-1The oxygen that volume ratio is 10: 90 and argon mixed gas, be warmed up to the speed of 2-10 DEG C/min
180-260 DEG C and at this temperature keep 15-36 minute；I.e. put into an air atmosphere after being taken out by this material, temperature constant is
The Muffle furnace of 800 DEG C keeps the 10-30 second, then takes out and in argon gas atmosphere, be cooled to room temperature under room temperature prepare Fe2O3|
FeF3-2xOx|Fe3+, Ce4+Doping fluorination zirconium layer structure lithium electricity positive electrode.
Fe the most according to claim 12O3|FeF3-2xOx|Fe3+, Ce4+Doping fluorination zirconium layer structure lithium electricity positive electrode, its feature
It is that above-mentioned zirconates is Zr (NO3)4·5H2O, ZrO (NO3)2·2H2One in O；Cerium salt is Ce (NH4)2(NO3)6、
Ce(SO4)2·4H2One in O；Iron salt is the one in Fe(NO3)39H2O, Iron(III) chloride hexahydrate；With fluorine as anion
Quaternary ammonium salt is the one in tetra-n-butyl ammonium fluoride, Methanaminium, N,N,N-trimethyl-, fluoride, benzyl trimethyl ammonium fluoride.
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| CN201610210101.0A Pending CN105914350A (en) | 2016-03-29 | 2016-03-29 | Fe2O3/FeF3-2xOx/Fe<3+>,Ce<4+> doped zirconium fluoride layer structure positive electrode material of lithium battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385200A (en) * | 2021-07-07 | 2021-09-14 | 浙江大学 | Full spectrum oxygen production CeF without sacrificial agent3alpha-FeOOH photocatalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140079998A1 (en) * | 2012-09-18 | 2014-03-20 | Honda Motor Co., Ltd. | Positive electrode active material for non-aqueous electrolyte secondary battery |
| CN104795538A (en) * | 2015-04-19 | 2015-07-22 | 宁波大学 | Solid-phase synthesis oxygen bearing bismuth fluoride anode material for lithium ion battery and preparation method thereof |
-
2016
- 2016-03-29 CN CN201610210101.0A patent/CN105914350A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140079998A1 (en) * | 2012-09-18 | 2014-03-20 | Honda Motor Co., Ltd. | Positive electrode active material for non-aqueous electrolyte secondary battery |
| CN104795538A (en) * | 2015-04-19 | 2015-07-22 | 宁波大学 | Solid-phase synthesis oxygen bearing bismuth fluoride anode material for lithium ion battery and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| HUI ZHOU ET. AL: "Controlled Formation of Mixed Nanoscale Domains of High Capacity Fe2O3-FeF3 Conversion Compounds by Direct Fluorination", 《ACS NANO》 * |
| 史月丽: "锂离子电池金属氟化物正极材料的制备及界面性能研究", 《中国博士学位论文全文数据库（电子期刊）工程科技II辑》 * |
| 张艳丽 等: "铁基氟化物锂电正极材料研究现状", 《储能科学与技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385200A (en) * | 2021-07-07 | 2021-09-14 | 浙江大学 | Full spectrum oxygen production CeF without sacrificial agent3alpha-FeOOH photocatalyst and preparation method thereof |
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