CN106972159A - A kind of continuous conduction original position C/ metal solid solutions/Zn2+Adulterate CuF2Positive pole and preparation method - Google Patents
A kind of continuous conduction original position C/ metal solid solutions/Zn2+Adulterate CuF2Positive pole and preparation method Download PDFInfo
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Abstract
A kind of continuous conduction original position C/ metal solid solutions/Zn2+Adulterate CuF2Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof; this method passes through the drying process under low temperature, high vacuum condition and the carbonization under gas shield and in-situ reducing process; form the continuous carbon film with hole and gap structure; and fixation forms copper fluoride and restores metal solid solution in the surface in situ of copper fluoride particle on the carbon film, plays the electronic conductivity for increasing substantially composite;Homogeneity crystallization nuclei is provided in electric discharge for electrode material, the dynamics of reduction New phase formation hinders;Pass through Zn2+Doping, reduces overpotential;It also avoid simultaneously and the side reaction products such as a variety of double salt of copper fluoride generated in liquid phase reactor and with excellent chemical property.
Description
Technical field
The present invention relates to a kind of electric positive electrode manufacture method technical field of high-performance copper fluoride complex lithium.
Background technology
Lithium rechargeable battery has volume, weight energy higher than high, voltage, low self-discharge rate, memory-less effect, circulation
Long lifespan, power density height etc. definitely advantage, had more than at present in global portable power source market 30,000,000,000 dollar/year shares and with
Speed more than 10% gradually increases.Particularly in recent years, petering out with fossil energy, solar energy, wind energy, biomass
The new energy such as energy are increasingly becoming the alternative of traditional energy, and wherein wind energy, solar energy has intermittence, to meet lasting electricity
Power supply needs to use substantial amounts of energy-storage battery simultaneously;The urban air-quality problem that vehicle exhaust is brought is increasingly serious, electronic
Very urgent stage has been arrived in vigorously advocating and developing for car (EV) or hybrid electric vehicle (HEV);These demands are provided
Lithium ion battery explosive growth point, while also the performance to lithium ion battery proposes higher requirement.
The raising of the capacity of anode material for lithium-ion batteries is the primary goal of scientific and technical personnel's research, high power capacity positive electrode
Research and development can to alleviate current Li-ion batteries piles volume big, heavy weight, price high-leveled and difficult to meet high power consumption and high-power equipment
The situation needed.But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time
Between 100-180mAh/g, the low bottleneck for having become lifting lithium ion battery specific energy of positive electrode specific capacity.It is commercial at present
The most commonly used practical positive electrode of lithium ion battery be LiCoO2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and
Actual specific capacity is between 130-140mAh/g, and cobalt is strategic materials, expensive and have larger toxicity.Therefore it is near
Nian Lai, the researcher of countries in the world is directed to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, to current, sieve
Up to tens of kinds of the lithium ion cell positive selected, but really have potential commercial applications prospect or be already present in the market
Positive electrode is really very few.Such as lithium manganate having spinel structure LiMn2O4, its cost is relatively low, is easier to prepare, security performance
Also 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 holds
Amount circulation holding capacity it is not good, under high temperature capacity attenuation quickly, Mn3+John-Teller effects and dissolving in the electrolyte
Researcher is annoying for a long time.The LiNiO of layer structure2And LiMnO2Although there is larger theoretical specific capacity, it is respectively
275mAh/g and 285 mAh/g, but they prepare extremely difficult, heat endurance is poor, and cyclicity is very poor, and capacity attenuation is quickly.
And progressively commercialized LiFePO4 LiFePO at present4Cost is low, heat endurance is good, environment-friendly, but its theory is held
Amount about only have 170 mAh/g, and actual capacity 140mAh/g or so [Chun SY, Bloking J T, Chiang Y M,
Nature Materials, 2002,1:123-128.].There is the positive pole material more than 200mAh/g specific capacities of market prospects at present
Material only has lithium vanadate Li1+xV3O8, Li1+xV3O8Material can have the capacity possessed even close to 300mAh/g, but its electric discharge is average
Voltage is relatively low and production process in barium oxide often toxicity is larger.High lithium is than on positive electrode in recent years, particularly manganese base
The high lithium of manganese-nickel binary and manganese base manganese-nickel-cobalt ternary solid solution system than positive electrode, with the Capacity Ratio more than 200mAh/g,
Higher heat endurance and the cost of relative moderate and paid close attention to by people, but the performance under the material high magnification is very not
Ideal, limits its application [Young-Sik Hong, Yong Joon Park, et al., Solid in electrokinetic cell
State Ionies, 2005,176:1035-1042].
In recent years, fluoride positive electrode is because its capacity is high, the prices of raw materials are low and enter the visual field of researcher.Fluorine
The operation principle of compound material and conventional lithium ion battery positive electrode is different, traditional lithium ion cell positive and negative pole
All exist lithium ion can be embedded in or deintercalation space, and lithium ion in electrolyte it is embedded back and forth between a positive electrode and a negative electrode and
Deintercalation and " rocking chair " battery proposed as Armand etc. that discharges.And fluoride is then a kind of transition material, that is, whole
In individual discharge process, although Me has nothing in common with each other, MeFnCan occur similar following change [Badway F, Cosandey F,
Pereira N, et al., Electrodes for Li Batteries, J.Electrochem.Soc., 2003,150 (10):
A1318-A1327.]:
nLi++MeFn+ne-→nLiF+Me0
It can discharge in this process and exceed well over 200mAh.g-1Specific capacity, thus it is high to obtain investigation of materials personnel
The attention of degree.Such as fluorination iron material has had many document reports, but often discharge curve does not have fluoride positive electrode
There is obvious platform, average discharge volt is low, energy density and power ratio are relatively low, such as be fluorinated the averaged discharge current potential of iron material
At 2.0 volts or so.But fluorination copper product has about 3.2V discharge platform voltage, all there is average voltage high and that capacity is big is excellent
Point.But it is also considerably less as the report of anode material for lithium-ion batteries on fluorination copper product, main difficulty is that fluorination
The chemical property of copper has close contact and poor repeatability with preparation process;Meanwhile, fluorination copper product is in organic electrolyte
Stability is also inadequate;It also has a negative characteristic to be exactly that electronic conductivity is extremely low, therefore can cause in charge and discharge process
Very high polarizing voltage, although have researcher and the electrical conductivity of material is improved using carbon black mixing and ball milling is added, but graininess
Carbon black be still difficult to form complete electrically conductive links, increase substantially its electronic conductivity.Finally, the material is produced in electric discharge
Raw metallic copper and lithium fluoride cenotype, cenotype small particles are kinetically being on a sticky wicket in the stage that originally forms, therefore to it
Charge/discharge capacity afterwards, discharge potential, the holding capacity of charge/discharge capacity can have a negative impact.Ion doping is also a kind of
The microstructure of effective regulation lattice, changes the means of lattice electron and ionic transport properties, however, ion doping is even
Polyion collaboration doping is extremely complex to the mechanism of action of parent, and effect is often difficult to expect.
Therefore exploitation one kind has complete conductive link, purity height, technical process is environment-friendly, product quality is stable, tool
The compound copper fluoride material preparation method for having excellent electrochemical performance is to be fluorinated the key that copper product is applied as secondary cell.
The content of the invention
The present invention proposes a kind of continuous conduction original position C/ metal solid solutions/Zn for existing background technology2+Adulterate CuF2
Compound copper fluoride anode material for lithium-ion batteries and preparation method thereof, this method passes through dried under low temperature, high vacuum condition
Journey, the reactants such as copper nitrate are fixed in the Continuous Polyacrylamide body for maintaining hole and gap structure and by liquid phase
In-situ preparation fluorination copper product is reacted, thereafter by the Continuous Polyacrylamide with hole and gap structure in heat treatment process
Entirety is transformed into the continuous carbon film with hole and gap structure, and the continuous carbon film structure has high conductive capability, significantly
Degree improves the electronic conductivity of composite;Simultaneously in heat treatment process copper fluoride particle surface reduction go out it is a certain amount of
Metal solid solution, homogeneity crystallization nuclei is provided for electrode material in electric discharge, and the dynamics for reducing New phase formation hinders, and carries
The high capacity of material, circulation volume stability and discharge platform current potential.Pass through Zn2+Doping, reduces overpotential;It is former by reacting
The immobilization of material, it is thus also avoided that the side reaction products such as a variety of double salt of copper fluoride are generated in liquid phase reactor and with excellent electricity
Chemical property.
This continuous conduction original position C/ metal solid solutions/Zn2+Adulterate CuF2Anode material for lithium-ion batteries and its preparation side
Method, it is characterized in that:It is 5-15wt% copper nitrates, 0.1-0.5wt% zinc nitrates, 6-12wt% acrylamides, 1- to prepare composition
2wt%N, N '-methylene-bisacrylamide starting aqueous solution, the quality of wherein acrylamide is N, N '-methylene bisacrylamide
6 times of acid amides quality, are stirred 5-15 minutes using Teflon stir oar with 900rpm-1200rpm speed.This is risen
The beginning aqueous solution rises to 75-85 DEG C with 5-10 DEG C/min of speed and keeps the temperature to turn into gelatin until starting aqueous solution
Gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying process can be used in the market
Finished product freeze drier, gel is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced in sample disc
Subzero 50 DEG C to subzero 45-, open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 25-35Pa in system, open
Baffle temperature control starts to dehydrate, and other operating parameters take machine preset value, treats that stable gas pressure drying terminates in system
Afterwards, it is saturated concentration 70-90% by material immersion concentration after drying, the amount of ammonium fluoride material is copper nitrate thing in starting aqueous solution
Stirred in the ammonium fluoride aqueous solution of 8-20 times of the amount of matter and in the case where Teflon stir oar is with 1000rpm-1200rpm speed
15-30 seconds, filter thereafter, in 0.1% hydrogen and 99.9% argon gas after being dried 3-7 hours in 80-120 DEG C of drying box
450-550 DEG C of constant temperature is warming up under mixed gas protected to cool down after 0.5-2 hours, prepares continuous conduction original position C/ metals
Solid solution/Zn2+Adulterate CuF2Compound copper fluoride anode material for lithium-ion batteries.
Compared with prior art, the advantage of the invention is that:This method passes through dried under low temperature, high vacuum condition
Journey, the reactants such as copper nitrate are fixed in the Continuous Polyacrylamide body for maintaining hole and gap structure and by liquid phase
In-situ preparation fluorination copper product is reacted, thereafter by the Continuous Polyacrylamide with hole and gap structure in heat treatment process
Entirety is transformed into the continuous carbon film with hole and gap structure, and the continuous carbon film structure has high conductive capability, significantly
Degree improves the electronic conductivity of composite;Simultaneously in heat treatment process copper fluoride particle surface reduction go out it is a certain amount of
Metal solid solution, homogeneity crystallization nuclei is provided for electrode material in electric discharge, and the dynamics for reducing New phase formation hinders, and carries
The high capacity of material, circulation volume stability and discharge platform current potential.Pass through Zn2+Doping, reduces overpotential;It is former by reacting
The immobilization of material, it is thus also avoided that the side reaction products such as a variety of double salt of copper fluoride are generated in liquid phase reactor and with excellent electricity
Chemical property.
Brief description of the drawings
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of Fig. 1 materials, voltage range 1.8V-
4.0V, charging and discharging currents 0.1C.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1:It is 5wt% copper nitrates, 0.1wt% zinc nitrates, 6wt% acrylamides, 1wt%N, N to prepare composition '-
The starting aqueous solution of methylene-bisacrylamide, is stirred 5 minutes using Teflon stir oar with 900rpm speed.Should
Starting aqueous solution rises to 75 DEG C with 5 DEG C/min of speed and keeps the temperature to be coagulated until starting aqueous solution turns into gelatin
Glue.The gel of formation is dried in the environment of low-temperature high-vacuum degree, 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 45 in sample disc
DEG C, open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 25Pa in system, open baffle temperature control and start to take off
Water is dried, and other operating parameters take machine preset value, and after stable gas pressure drying terminates in system, material after drying is immersed
Concentration is saturated concentration 70%, and the amount of ammonium fluoride material is that the ammonium fluoride of 8 times of the amount of nitric acid copper material in starting aqueous solution is water-soluble
Stir 15 seconds, filter thereafter in liquid and in the case where Teflon stir oar is with 1000rpm speed, done in 80 DEG C of drying box
After dry 3 hours 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 450 DEG C of constant temperature 0.5 hour after cool down,
Prepare continuous conduction original position C/ metal solid solutions/Zn2+Adulterate CuF2Compound copper fluoride anode material for lithium-ion batteries.
Embodiment 2:Composition is prepared for 15wt% copper nitrates, 0.5wt% zinc nitrates, 12wt% acrylamides, 2wt%N,
The starting aqueous solution of N '-methylene-bisacrylamide, 15 points are stirred using Teflon stir oar with 1200rpm speed
Clock.The starting aqueous solution is risen to 85 DEG C with 10 DEG C/min of speed and keeps the temperature to turn into glue until starting aqueous solution
Freeze the gel of shape.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying process is used in the market
Finished product freeze drier, gel is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced in sample disc
To subzero 50 DEG C, open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 32Pa 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 90%, and the amount of ammonium fluoride material is the fluorine of 18 times of the amount of nitric acid copper material in starting aqueous solution
Change in aqueous ammonium and stirred 30 seconds in the case where Teflon stir oar is with 1200rpm speed, filtered thereafter, at 120 DEG C
After being dried 7 hours in drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under to be warming up to 550 DEG C of constant temperature 2 small
When after cool down, prepare continuous conduction original position C/ metal solid solutions/Zn2+Adulterate CuF2Compound copper fluoride lithium ion cell positive
Material.
Embodiment 3:Composition is prepared for 7wt% copper nitrates, 0.3wt% zinc nitrates, 9wt% acrylamides, 1.5wt%N,
The starting aqueous solution of N '-methylene-bisacrylamide, 10 points are stirred using Teflon stir oar with 1150rpm speed
Clock.The starting aqueous solution is risen to 80 DEG C with 7 DEG C/min of speed and keeps the temperature to turn into jelly until starting aqueous solution
The gel of shape.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying process using in the market into
Product freeze drier, gel is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced in sample disc
Subzero 48 DEG C, open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 30Pa in system, open baffle temperature control
Start to dehydrate, other operating parameters take machine preset value, after stable gas pressure drying terminates in system, by thing after drying
Material immersion concentration is saturated concentration 80%, and the amount of ammonium fluoride material is the fluorination of 15 times of the amount of nitric acid copper material in starting aqueous solution
Stir 25 seconds, filter thereafter in aqueous ammonium and in the case where Teflon stir oar is with 1100rpm speed, in 100 DEG C do
After being dried 5 hours in dry case 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 500 DEG C of constant temperature 1 hour
After cool down, prepare continuous conduction original position C/ metal solid solutions/Zn2+Adulterate CuF2Compound copper fluoride lithium ion cell positive material
Material.
Embodiment 4:It is 5wt% copper nitrates, 0.2wt% zinc nitrates, 12wt% acrylamides, 2wt%N, N to prepare composition '-
The starting aqueous solution of methylene-bisacrylamide, is stirred 8 minutes using Teflon stir oar with 1200rpm speed.Will
The starting aqueous solution rises to 82 DEG C with 8 DEG C/min of speed and keeps the temperature to turn into gelatin until starting aqueous solution
Gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, 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 85%, the amount of ammonium fluoride material is the ammonium fluoride water of 20 times of the amount of nitric acid copper material in starting aqueous solution
Stir 25 seconds, filter thereafter, in 110 DEG C of drying box in solution and in the case where Teflon stir oar is with 1100rpm speed
After middle drying 7 hours 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 500 DEG C of constant temperature 1.5 hours after
Cooling, prepares continuous conduction original position C/ metal solid solutions/Zn2+Adulterate CuF2Compound copper fluoride lithium ion cell positive material
Material.
Embodiment 5:Composition is prepared for 15wt% copper nitrates, 0.4wt% zinc nitrates, 12wt% acrylamides, 2wt%N,
The starting aqueous solution of N '-methylene-bisacrylamide, 12 points are stirred using Teflon stir oar with 1100rpm speed
Clock.80 DEG C will be risen to 10 DEG C/min of speed and keep the temperature to turn into glue until starting aqueous solution to starting aqueous solution
Freeze the gel of shape.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying process is used in the market
Finished product freeze drier, gel is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced in sample disc
To subzero 46 DEG C, open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 32Pa 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 85%, and the amount of ammonium fluoride material is the fluorine of 16 times of the amount of nitric acid copper material in starting aqueous solution
Change in aqueous ammonium and stirred 17 seconds in the case where Teflon stir oar is with 1120rpm speed, filtered thereafter, at 110 DEG C
After being dried 6 hours in drying box 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under to be warming up to 550 DEG C of constant temperature 2 small
When after cool down, prepare continuous conduction original position C/ metal solid solutions/Zn2+Adulterate CuF2Compound copper fluoride lithium ion cell positive
Material.
Claims (1)
1. a kind of continuous conduction original position C/ metal solid solutions/Zn2+Adulterate CuF2The preparation method of anode material for lithium-ion batteries, its
It is characterized as:Composition is prepared for 5-15wt% copper nitrates, 0.1-0.5wt% zinc nitrates, 6-12wt% acrylamides, 1-2wt%N,
The quality of the starting aqueous solution of N '-methylene-bisacrylamide, wherein acrylamide is N, N '-methylene-bisacrylamide quality
6 times, stirred 5-15 minutes with 900rpm-1200rpm speed 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 to turn into gelatin gel until starting aqueous solution;By shape
Into gel on finished product freeze drier in the market dry, by gel be put into freeze drier sample disc start make
Cold, treats that gelling temp is reduced to subzero 50 DEG C of subzero 45- in sample disc, opens vavuum pump and improve vacuum, treat gas in system
Body pressure is reduced to below 25-35Pa, opens baffle temperature control and starts to dehydrate, 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 nitric acid copper material in starting aqueous solution and in Teflon stir oar
To be stirred 15-30 seconds under 1000rpm-1200rpm speed, filter thereafter, dried 3-7 hours in 80-120 DEG C of drying box
Afterwards 0.1% hydrogen and 99.9% argon gas it is mixed gas protected under be warming up to 450-550 DEG C of constant temperature 0.5-2 hours after cool down,
Prepare continuous conduction original position C/ metal solid solutions/Zn2+Adulterate CuF2Compound copper fluoride anode material for lithium-ion batteries.
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Citations (1)
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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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CN102344151A (en) * | 2011-06-23 | 2012-02-08 | 中山大学 | Prussian blue nano-scale hollow olivary microballoons |
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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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Application publication date: 20170721 |