CN106848265A - A kind of monolithic conductive original position C/Bi, Ag/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method - Google Patents
A kind of monolithic conductive original position C/Bi, Ag/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method Download PDFInfo
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- CN106848265A CN106848265A CN201710213057.3A CN201710213057A CN106848265A CN 106848265 A CN106848265 A CN 106848265A CN 201710213057 A CN201710213057 A CN 201710213057A CN 106848265 A CN106848265 A CN 106848265A
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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
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Abstract
A kind of monolithic conductive original position C/Bi, Ag/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method thereof, be fixed on bismuth nitrate on the continuous carbon film of high conductivity with hole and gap structure by drying process and heat treatment process under low temperature, high vacuum condition by the method；The surface reduction in fluorination bismuth particle in heat treatment process goes out a certain amount of bismuth metal and silver simultaneously, and bismuth provides homogeneity crystallization nuclei for electrode material in electric discharge, and the dynamics for reducing New phase formation hinders；Silver is favorably improved exoelectrical reaction speed；Also by the immobilization of reaction raw materials, it is to avoid the side reaction products such as various double salt of fluorination bismuth are generated in liquid phase reactor and with excellent chemical property.
Description
Technical field
The present invention relates to a kind of high-performance fluorination bismuth complex lithium electricity positive electrode manufacture method technical field.
Background technology
Lithium rechargeable battery has volume, weight energy higher than high, voltage, low self-discharge rate, memory-less effect, circulation
Long lifespan, the power density definitely advantage such as high, at present global portable power source market have more than 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 brings 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 requirement higher.
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 power consumption high and high-power equipment
The situation of needs.But since lithium ion battery in 1991 is commercialized, 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 devoted 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 for going 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
Circulation 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 having larger theoretical specific capacity, respectively
275mAh/g and 285mAh/g, but they prepare extremely difficult, and heat endurance is poor, and cyclicity is very poor, and capacity attenuation is quickly.And
Progressively commercialized LiFePO4 LiFePO at present4Low cost, heat endurance are good, environment-friendly, but its 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 possess even close to 300mAh/g capacity, but its electric discharge average voltage it is relatively low and
And in production process barium oxide often toxicity is larger.Lithium high is than on positive electrode in recent years, particularly manganese base manganese-nickel binary and
The lithium high of manganese base manganese-nickel-cobalt ternary solid solution system is steady with the Capacity Ratio more than 200mAh/g, heat higher 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 enters the visual field of researcher because its capacity is high, the prices of raw materials are low.Fluorine
Compound material is different with the operation principle of conventional lithium ion battery positive electrode, 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
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 cannot often be used as positive electrode simultaneously because being hydrolyzed in water to suppress bismuth nitrate because by-products content is too high
And the dust technology for adding has the risk that high toxicity hydrogen fluoride is produced with ammonium fluoride effect.Fluorination bismuth is used as lithium ion secondary electricity
It is extremely low its electronic conductivity that pond positive electrode also has a negative characteristic, therefore can be caused in charge and discharge process very high
Polarizing voltage.Although having researcher improves the electrical conductivity of material using carbon black mixing and ball milling is added, but granular charcoal
It is black to be still difficult to form complete electrically conductive links, increase substantially its electronic conductivity.Finally, the material produces gold in electric discharge
Category bismuth and lithium fluoride cenotype, cenotype small particles in the stage that originally forms being kinetically on a sticky wicket, therefore to thereafter
Charge/discharge capacity, discharge potential, the holding capacity of charge/discharge capacity can have a negative impact.
Therefore exploitation one kind has complete conductive link, purity is high, technical process is environment-friendly, product quality is stable, tool
The compound fluorination bismuth material preparation method for having excellent electrochemical performance is the key for being fluorinated bismuth material as secondary cell application.
The content of the invention
The present invention proposes a kind of monolithic conductive original position C/Bi, Ag/BiF for existing background technology3Compound fluorination bismuth lithium
Ion battery positive electrode and preparation method thereof, the method is consolidated bismuth nitrate by the drying process under low temperature, high vacuum condition
It is scheduled in the Continuous Polyacrylamide body for maintaining hole and gap structure and bismuth material is fluorinated by liquid phase reactor in-situ preparation
Material, the Continuous Polyacrylamide with hole and gap structure is integrally transformed into hole in heat treatment process thereafter and
The continuous carbon film of gap structure, the continuous carbon film structure has high conductive capability, increases substantially the electronics of composite
Electrical conductivity；Go out a certain amount of bismuth metal and silver in the surface reduction of fluorination bismuth particle in heat treatment process simultaneously, bismuth metal is
Electrode material provides homogeneity crystallization nuclei in electric discharge, and the dynamics for reducing New phase formation hinders, and improves the appearance of material
Amount, circulation volume stability and discharge platform current potential；Silver is favorably improved exoelectrical reaction speed.By the fixation of reaction raw materials
Change, it is thus also avoided that the side reaction products such as various double salt of fluorination bismuth are generated in liquid phase reactor and there is excellent electrochemistry
Energy.
This monolithic conductive original position C/Bi, Ag/BiF3Compound fluorination bismuth anode material for lithium-ion batteries and preparation method thereof,
It is characterized by：It is 5-15wt% bismuth nitrates, 0.5-1wt% nitric acid, 6-12wt% acrylamides, 1-2wt%N, N to prepare composition '-
The quality of the starting aqueous solution of methylene-bisacrylamide, wherein acrylamide is N, the 6 of N '-methylene-bisacrylamide quality
Times, stirred 5-15 minutes with the speed of 900rpm-1200rpm using Teflon stir oar.By the starting aqueous solution with 5-
10 DEG C/min of speed rises to 75-85 DEG C and keeps the temperature until starting aqueous solution is as gelatin gel.To be formed
Gel dried in the environment of low-temperature high-vacuum degree, the drying process can be using finished product freeze-drying in the market
Machine, gel is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced to subzero 45 DEG C-zero in sample disc
Lower 50 DEG C, open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 25-35Pa in system, opens baffle temperature control
System starts to dehydrate, and other operating parameters take machine preset value, after stable gas pressure drying terminates in system, after drying
Material immersion concentration is saturated concentration 70-90%, and the amount of ammonium fluoride material is the amount 8-20 of bismuth nitrate material in starting aqueous solution
Stirred 15-30 seconds in ammonium fluoride aqueous solution again and in the case where Teflon stir oar is with the speed of 1000rpm-1200rpm, its
After filter, dry 3-7 hours in 80-120 DEG C of drying box, immerse in saturation silver nitrate solution kept for 10-15 minutes afterwards
After filter, dried in 80-120 DEG C of drying box 3-5 hours, thereafter in 0.5% hydrogen and the mixed gas of 99.5% argon gas
450-550 DEG C is warmed up under protection to cool down after constant temperature 0.5-2 hours, prepares monolithic conductive original position C/Bi, Ag/BiF3It is compound
Fluorination bismuth anode material for lithium-ion batteries.
Compared with prior art, the advantage of the invention is that：The method is by dried under low temperature, high vacuum condition
Journey, bismuth nitrate is fixed in the Continuous Polyacrylamide body for maintaining hole and gap structure and in situ by liquid phase reactor
Generation fluorination bismuth material, thereafter integrally changes the Continuous Polyacrylamide with hole and gap structure in heat treatment process
Into the continuous carbon film with hole and gap structure, the continuous carbon film structure has high conductive capability, increases substantially multiple
The electronic conductivity of condensation material；Simultaneously in heat treatment process fluorination bismuth particle surface reduction go out a certain amount of bismuth metal and
Silver, bismuth metal provides homogeneity crystallization nuclei for electrode material in electric discharge, and the dynamics for reducing New phase formation hinders, and improves
The capacity of material, circulation volume stability and discharge platform current potential；Silver is favorably improved exoelectrical reaction speed.It is former by reacting
The immobilization of material, it is thus also avoided that the side reaction products such as various double salt of fluorination bismuth are generated in liquid phase reactor and there is excellent electricity
Chemical property.
Brief description of the drawings
The charging capacity of preceding 10 circulations of Fig. 1 materials, discharge capacity and efficiency for charge-discharge figure, voltage range 1.8V-
4.0V, charging and discharging currents 0.1C.
Specific embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1：It is 5wt% bismuth nitrates, 0.5wt% nitric acid, 6wt% acrylamides, 1wt%N, N to prepare composition '-sub-
The starting aqueous solution of bisacrylamide, is stirred 5 minutes using Teflon stir oar with the speed of 900rpm.By starting
The aqueous solution rises to 75 DEG C and keeps the temperature until starting aqueous solution is as gelatin gel with 5 DEG C/min of speed.Will
The gel of formation is dried in the environment of low-temperature high-vacuum degree, and the drying process is using finished product freeze-drying in the market
Machine, gel is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced to subzero 46 DEG C in sample disc, opens
Open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 27Pa in system, open baffle temperature and control to start to be dehydrated to do
Dry, other operating parameters take machine preset value, after stable gas pressure drying terminates in system, by material immersion concentration after drying
It is saturated concentration 70%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 8 times of the amount of bismuth nitrate material in starting aqueous solution
And stirred 15 seconds in the case where Teflon stir oar is with 1100 speed, filter thereafter, 3 are dried in 80 DEG C of drying box small
When, immerse filtered after being kept for 10 minutes in saturation silver nitrate solution afterwards, dried 3 hours in 80 DEG C of drying box, exist thereafter
0.5% hydrogen and 99.5% argon gas it is mixed gas protected under be warmed up to 450 DEG C of constant temperature and cooled down after 0.5 hour, prepare whole
Body conduction original position C/Bi, Ag/BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
Embodiment 2：Prepare composition 15wt% bismuth nitrates, 1wt% nitric acid, 12wt% acrylamides, 2wt%N, N '-methylene
The starting aqueous solution of base bisacrylamide, is stirred 14 minutes using Teflon stir oar with the speed of 1200rpm.By starting
The aqueous solution rises to 85 DEG C and keeps the temperature until starting aqueous solution is as gelatin gel with 10 DEG C/min of speed.
The gel that will be formed is dried in the environment of low-temperature high-vacuum degree, and the drying process is using finished product freeze-drying in the market
Machine, gel is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced to subzero 50 DEG C in sample disc, opens
Open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 34Pa in system, open baffle temperature and control to start to be dehydrated to do
Dry, other operating parameters take machine preset value, after stable gas pressure drying terminates in system, by material immersion concentration after drying
It is saturated concentration 88%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 20 times of the amount of bismuth nitrate material in starting aqueous solution
And stirred 30 seconds in the case where Teflon stir oar is with the speed of 1200rpm, filter thereafter, 7 are dried in 115 DEG C of drying box
Hour, immerse filtered after being kept for 15 minutes in saturation silver nitrate solution afterwards, it is dry 5 hours in 120 DEG C of drying box, thereafter
0.5% hydrogen and 99.5% argon gas it is mixed gas protected under be warmed up to 550 DEG C of constant temperature 2 hours after cool down, prepare whole
Body conduction original position C/Bi, Ag/BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
Embodiment 3：It is 12wt% bismuth nitrates, 0.8wt% nitric acid, 9wt% acrylamides, 1.5wt%N, N to prepare composition '-
The starting aqueous solution of methylene-bisacrylamide, is stirred 9 minutes using Teflon stir oar with the speed of 1100rpm.Will
Starting aqueous solution rises to 80 DEG C and keeps the temperature to be coagulated until starting aqueous solution turns into gelatin with 7 DEG C/min of speed
Glue.The gel that will be formed is dried in the environment of low-temperature high-vacuum degree, and the drying process is using finished product freezing in the market
Drying machine, gel is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced to subzero 48 in sample disc
DEG C, open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 30Pa in system, open baffle temperature control and start to take off
Water is dried, and other operating parameters take machine preset value, after stable gas pressure drying terminates in system, material after drying is immersed
Concentration is saturated concentration 80%, and the amount of ammonium fluoride material is that the ammonium fluoride of 15 times of the amount of bismuth nitrate material in starting aqueous solution is water-soluble
Stirred 25 seconds in liquid and in the case where Teflon stir oar is with the speed of 1150rpm, filtered thereafter, in 100 DEG C of drying box
Dry 5 hours, immerse filtered after being kept for 12 minutes in saturation silver nitrate solution afterwards, 4 are dried in 100 DEG C of drying box small
When, thereafter 0.5% hydrogen and 99.5% argon gas it is mixed gas protected under be warmed up to 500 DEG C of constant temperature 1 hour after cool down, prepare
Obtain monolithic conductive original position C/Bi, Ag/BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
Embodiment 4：It is 5wt% bismuth nitrates, 1wt% nitric acid, 12wt% acrylamides, 2wt%N, N to prepare composition '-methylene
The starting aqueous solution of base bisacrylamide, is stirred 10 minutes using Teflon stir oar with the speed of 1000rpm.By starting
The aqueous solution rises to 80 DEG C and keeps the temperature until starting aqueous solution is as gelatin gel with 7 DEG C/min of speed.Will
The gel of formation is dried in the environment of low-temperature high-vacuum degree, and the drying process is using finished product freeze-drying in the market
Machine, gel is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced to subzero 48 DEG C in sample disc, opens
Open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 30Pa in system, open baffle temperature and control to start to be dehydrated to do
Dry, other operating parameters take machine preset value, after stable gas pressure drying terminates in system, by material immersion concentration after drying
It is saturated concentration 80%, the amount of ammonium fluoride material is in the ammonium fluoride aqueous solution of 10 times of the amount of bismuth nitrate material in starting aqueous solution
And stirred 22 seconds in the case where Teflon stir oar is with the speed of 1150rpm, filter thereafter, 5 are dried in 110 DEG C of drying box
Hour, immerse filtered after being kept for 10 minutes in saturation silver nitrate solution afterwards, it is dry 3 hours in 80 DEG C of drying box, thereafter
0.5% hydrogen and 99.5% argon gas it is mixed gas protected under be warmed up to 520 DEG C of constant temperature 1 hour after cool down, prepare whole
Body conduction original position C/Bi, Ag/BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
Embodiment 5：Composition is prepared for 7.5wt% bismuth nitrates, 0.7wt% nitric acid, 9wt% acrylamides, 1.5wt%N,
The starting aqueous solution of N '-methylene-bisacrylamide, is stirred 8 minutes using Teflon stir oar with the speed of 1100rpm.
By starting aqueous solution with 9 DEG C/min of speed rise to 81 DEG C and keep the temperature until starting aqueous solution turn into it is gelatin
Gel.The gel that will be formed is dried in the environment of low-temperature high-vacuum degree, and the drying process is cold using finished product in the market
Lyophilizer, gel is put into freeze drier sample disc and starts refrigeration machine, treats in sample disc that gelling temp is reduced to subzero
49 DEG C, open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 30Pa in system, open baffle temperature control and start
Dehydrate, other operating parameters take machine preset value, after stable gas pressure drying terminates in system, material after drying is soaked
Enter concentration for saturated concentration 80%, the amount of ammonium fluoride material is the ammonium fluoride water of 15 times of the amount of bismuth nitrate material in starting aqueous solution
Stirred 25 seconds in solution and in the case where Teflon stir oar is with the speed of 1120rpm, filtered thereafter, in 100 DEG C of drying box
Middle drying 5 hours, immerses filtered after being kept for 10 minutes in saturation silver nitrate solution afterwards, 5 is dried in 90 DEG C of drying box small
When, thereafter 0.5% hydrogen and 99.5% argon gas it is mixed gas protected under be warmed up to 550 DEG C of constant temperature 1.5 hours after cool down, system
It is standby to obtain monolithic conductive original position C/Bi, Ag/BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
Claims (1)
1. a kind of monolithic conductive original position C/Bi, Ag/BiF3The preparation method of compound fluorination bismuth anode material for lithium-ion batteries, it is special
Levy for：It is 5-15wt% bismuth nitrates, 0.5-1wt% nitric acid, 6-12wt% acrylamides, 1-2wt%N, N to prepare composition '-methylene
The quality of the starting aqueous solution of base bisacrylamide, wherein acrylamide is N, 6 times of N '-methylene-bisacrylamide quality,
Stirred 5-15 minutes with the speed of 900rpm-1200rpm using Teflon stir oar；By the starting aqueous solution with 5-10
DEG C/min speed rise to 75-85 DEG C and keep the temperature until starting aqueous solution turn into gelatin gel；By what is formed
Gel is dried on finished product freeze drier in the market, gel is put into freeze drier sample disc and starts refrigeration
Machine, treats that gelling temp is reduced to subzero 45 DEG C-subzero 50 DEG C in sample disc, opens vavuum pump and improves vacuum, treats gas in system
Body pressure is reduced to below 25-35Pa, opens baffle temperature control and starts to dehydrate, and other operating parameters take machine to preset
Value, is saturated concentration 70-90%, ammonium fluoride thing by material immersion concentration after drying after stable gas pressure drying terminates in system
The amount of matter is in the ammonium fluoride aqueous solution of 8-20 times of the amount of bismuth nitrate material in starting aqueous solution and in Teflon stir oar
Stirred 15-30 seconds with the speed of 1000rpm-1200rpm, filtered thereafter, it is small to dry 3-7 in 80-120 DEG C of drying box
When, immerse filtered after being kept for 10-15 minutes in saturation silver nitrate solution afterwards, it is small to dry 3-5 in 80-120 DEG C of drying box
When, thereafter 0.5% hydrogen and 99.5% argon gas it is mixed gas protected under be warmed up to 450-550 DEG C after constant temperature 0.5-2 hours
Cooling, prepares monolithic conductive original position C/Bi, Ag/BiF3Compound fluorination bismuth anode material for lithium-ion batteries.
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| CN102344151A (en) * | 2011-06-23 | 2012-02-08 | 中山大学 | Prussian blue nano-scale hollow olivary microballoons |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344151A (en) * | 2011-06-23 | 2012-02-08 | 中山大学 | Prussian blue nano-scale hollow olivary microballoons |
Non-Patent Citations (2)
| Title |
|---|
| 中南矿冶学院《冶金过程原理》编写小组: "《冶金过程原理》", 30 September 1973 * |
| 张海波 等: ""聚丙烯酰胺的合成及应用研究进展"", 《高分子材料科学与工程》 * |
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