CN106898771A - Lithium-iron disulphide anode material of lithium battery - Google Patents
Lithium-iron disulphide anode material of lithium battery Download PDFInfo
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- CN106898771A CN106898771A CN201710289195.XA CN201710289195A CN106898771A CN 106898771 A CN106898771 A CN 106898771A CN 201710289195 A CN201710289195 A CN 201710289195A CN 106898771 A CN106898771 A CN 106898771A
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/5815—Sulfides
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- H01M10/00—Secondary cells; Manufacture thereof
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- H—ELECTRICITY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a kind of lithium-iron disulphide anode material of lithium battery, its positive active material for including modified ferrous disulfide, the positive active material is the ferrous disulfide doped with the titanium oxide, 4% magnesia and 6% cupric oxide that mass percent is 2%, and the positive active material preparation method is specially：A) first part of heat treatment ferrous disulfide, second part of heat treatment ferrous disulfide and the 3rd part of heat treatment ferrous disulfide are prepared；B) prepare first and coat ferrous disulfide, the second cladding ferrous disulfide and the 3rd cladding ferrous disulfide；C) ferrous disulfide, the second cladding ferrous disulfide and the 3rd cladding ferrous disulfide are coated by first and is well mixed to obtain lithium-iron disulphide anode material of lithium battery.The present invention can reduce the open-circuit voltage of battery so that voltage platform is more steady；In addition combined conductive agent is also added into positive electrode, electric conductivity can be greatly improved, reduce the polarization of battery, improve the high temperature performance of battery, extend the life-span of battery.
Description
Technical field
The present invention relates to lithium battery material technical field.It is more particularly related to one kind is modified by adding
Ferrous disulfide obtain lithium-iron disulfide anode material of lithium battery.
Background technology
Battery of lithium-iron disulphide is that, with ferrous disulfide as positive active material, lithium ion is the high energy of negative electrode active material
Environmentally friendly one-shot battery, with many advantages that traditional one-shot battery can not compare：Discharge voltage is high and more steady；Discharge capacity
Greatly；Specific power is high, discharge current is big；Weight is most light in the battery product of same model；Operating temperature range is wider；High temperature storage
It is functional；There is good preventing liquid leakage performance；Storage life is long；Battery mercury-free, without cadmium, unleaded, be environmental protection, safe and reliable
Novel energy storage apparatus.Because of its excellent performance, lithium-iron disulfide using wide, is currently used primarily in daily life
Digital camera, MP3, handheld game machine, portable CD Player, palm PC, digital display instrument, medicine equipment, all kinds of ammeters,
Water meter etc., also has potential application prospect more very in the military fields such as weaponry, Aero-Space.
With the progress of development in science and technology, the demand to battery of lithium-iron disulphide is increasing, and performance requirement is also increasingly
Height, improving and upgrading for electrode material turns into battery of lithium-iron disulphide performance development with the break-through point of research, particularly positive pole material
Material is as one of most important part in research.The positive electrode ferrous disulfide of battery of lithium-iron disulphide is typically from Huang
Separated in iron ore, purification is obtained, its open-circuit voltage of the ferrous disulfide for just obtaining is assembled as material battery is higher, voltage platform
It is poor with heavy-current discharge performance, to improve voltage platform and discharge performance, it is necessary to be modified to active material ferrous disulfide
Treatment, it is single to there is to the treatment of ferrous disulfide method in existing technology, the problems such as DeGrain and cumbersome complex process；
Additionally, the quality of the performance of the conductive agent of one of composition as positive electrode also has of crucial importance to the discharge performance of battery
Influence.
The content of the invention
It is an object of the invention to solve at least the above, and provide the advantage that at least will be described later.
It is a still further object of the present invention to provide a kind of lithium-iron disulfide anode material of lithium battery, the present invention is by by just
In batches, and it is different with introducing that the heat treatment of different temperatures is carried out to the ferrous disulfide of different batches for the isolated ferrous disulfide of step
Metal oxide, obtains three kinds of crystal phase structure, granular size modified ferrous disulfides different with surface texture, and modified by three kinds
Ferrous disulfide be well mixed, the active material of obtained ferrous disulfide can reduce battery as the material of lithium-iron disulfide
Open-circuit voltage so that voltage platform is more steady；In addition combined conductive agent is also added into positive electrode, can be carried significantly
High conductivity, reduces the polarization of battery, improves the high temperature performance of battery, extends the life-span of battery.
In order to realize these purposes of the invention and further advantage, there is provided a kind of lithium-iron disulfide lithium battery is just
Pole material, its positive active material for including modified ferrous disulfide, the positive active material is doped with mass percent
It is the ferrous disulfide of 2% titanium oxide, 4% magnesia and 6% cupric oxide, the positive active material preparation method is specific
For：
A) ferrous disulfide that the separating-purifying from pyrite is obtained is divided into three equal parts, by the ferrous disulfide of three equal parts point
It is not put into the electric heating constant-temperature blowing drying box that temperature is 250 DEG C, 300 DEG C and 380 DEG C, taking-up is cooled to room temperature after preserving 24h,
First part of heat treatment ferrous disulfide, second part of heat treatment ferrous disulfide and the 3rd part of heat treatment ferrous disulfide are obtained, period is to three
Nitrogen is passed through in drying box；
B) first part of heat treatment ferrous disulfide is scattered in 2~4h of ball milling in absolute ethyl alcohol, is then placed in 70~80 DEG C
Dried in vacuum drying chamber, then drying object is scattered in deionized water, and be added thereto to slaine titanium tetrachloride solution
With ammoniacal liquor mixed solution, it is sufficiently stirred for filtering after 4~6h, collects the first filter residue and with absolute ethanol washing 1~3 time, will washs
The first filter residue afterwards is dried in being put into 70~80 DEG C of vacuum drying chamber, is then located in 180~240 DEG C of high temperature inert gas
1~3h of reason, obtains the first cladding ferrous disulfide；Second part of heat treatment ferrous disulfide is scattered in ball milling 2~4h, Ran Houfang in acetone
Enter drying in 70~80 DEG C of vacuum drying chamber, then drying object is scattered in deionized water, and be added thereto to slaine
Magnesium chloride solution and ammoniacal liquor mixed solution, filter after being sufficiently stirred for 4~6h, collect the second filter residue and are washed with acetone 1~3 time,
The second filter residue after by washing is dried in being put into 70~80 DEG C of vacuum drying chamber, then in 240~280 DEG C of high temperature inert gas
1~3h is processed in body, the second cladding ferrous disulfide is obtained；3rd part of heat treatment ferrous disulfide is scattered in ball in dimethylformamide
2~4h of mill, is then placed in being dried in 170~220 DEG C of vacuum drying chamber, and then drying object is scattered in deionized water, and
Slaine copper-bath and ammoniacal liquor are added thereto to, are filtered after being sufficiently stirred for 4~6h, collected the 3rd filter residue and use absolute ethyl alcohol
Washing 1~3 time, by washing after the 3rd filter residue be put into 170~220 DEG C of vacuum drying chamber and dry, then 300~340
DEG C high temperature inert gas in process 1~3h, obtain the 3rd cladding ferrous disulfide；
C) ferrous disulfide, the second cladding ferrous disulfide and the 3rd cladding ferrous disulfide is coated by described first to put
Enter in the ball grinder of polytetrafluoroethylene (PTFE), be added thereto to the absolute ethyl alcohol ball milling 3 of described first cladding, 3.2 times of weight of ferrous disulfide
, then be placed in the material in ball grinder in vacuum drying chamber by~5h, 2~4h of constant temperature at 70~80 DEG C, takes out dried object and is placed in
Grind into powder in grinding alms bowl, obtains final product.
Preferably, described lithium-iron disulfide anode material of lithium battery, also including conductive agent, it is that weight ratio is 1:
2:The compound that 3 carbon fibers, CNT and carbon black are formed；The preparation method of the conductive agent is specially：Carbon black is divided into weight
Amount is than being 2:First part of 1 and second part, first part of carbon black and CNT are placed in the ball grinder equipped with absolute ethyl alcohol, ball
Taken out after mill 2h, be put into 100 DEG C of vacuum drying chamber and dry 10h, obtain the first conductive material；By second part of carbon black and carbon fiber
It is put into the ball grinder equipped with absolute ethyl alcohol, is taken out after ball milling 2h, be put into 100 DEG C of vacuum drying chamber and dry 10h, obtains second
Conductive material；First conductive material and the second conductive material are poured into the dimethyl sulphoxide solution dissolved with gelatin, high-speed stirred
Filtered after 40~60min, filtrate is washed 1~3 time with acetone and ethanol respectively, be then placed in 100 DEG C of vacuum drying chamber
Middle 4~6h of drying, obtains final product the conductive agent.
Preferably, described lithium-iron disulfide anode material of lithium battery, also including binding agent, it includes that weight ratio is
3:1:1 butadiene-styrene rubber, sodium carboxymethylcellulose and polymethylacrylic acid.
Preferably, described lithium-iron disulfide anode material of lithium battery, also including dispersant, the dispersant includes
Weight ratio is 2:1 polyethylene glycol and polyvinyl alcohol.
Preferably, described lithium-iron disulfide anode material of lithium battery, also including solvent, the solvent is N- methyl
Pyrrolidones.
Preferably, described lithium-iron disulfide anode material of lithium battery, the positive active material, the conductive agent,
The mass ratio 90.8 of the binding agent and the dispersant:3.1~4.5:3.1~4.5:0.9~1.5, the solvent with it is described
The mass ratio of positive active material is 2.5:1.
Preferably, described lithium-iron disulfide anode material of lithium battery, the preparation method of the carbon fiber is：By weight
Amount number meter, takes 30~40 parts of acetic acid lignins, and 20~28 parts of alkaline lignin is dissolved in 100 parts of acetic acid solution respectively,
The first solution and the second solution are configured, to the metallic nickel that 0.01~0.03 part is added in first solution, the first spinning solution is obtained；
0.01~0.03 part of metallic copper is added in second solution, the second spinning solution is obtained；By first spinning solution and described
Two spinning solutions are placed in high-voltage electrostatic spinning device, carry out electrostatic spinning, obtain the first nanofiber and the second nanofiber, will
First nanofiber and the mixing of the second nanofiber are pre-oxidized in being put into Muffle furnace, then by the nanofiber after pre-oxidation
Mixture is warming up to 700 DEG C under putting nitrogen protection, and heating rate is 100 DEG C/h, and room temperature is cooled to after carbonization treatment 1h, and crushing is
Obtain the carbon fiber.
The present invention at least includes following beneficial effect：
1st, heat treatment be able to can also be increased by the content that removes the moisture in ferrous disulfide to improve ferrous disulfide in mineral
The specific surface area of big ferrous disulfide, the increase of specific surface area can improve the positive electrode of lithium-iron disulfide lithium battery to electrolyte
Absorptivity, the increase of ferrous disulfide content and the increase to the absorptivity of electrolyte can increase the discharge capacity of battery, carry
The performance of lithium battery is risen, but heat treatment can increase the bulk density of ferrous disulfide, and temperature more high-bulk-density is bigger, piles up close
Spending conference causes active material to mix uneven problem with conductive agent, binding agent；The present invention will be separated, two that purification is obtained
Iron sulfide is divided into three equal parts, three equal parts is carried out with the heat treatment of different temperatures, and the ferrous disulfide after three equal parts heat treatment is entered
The cladding of row different metal oxides, the ferrous disulfide of three kinds of different modifications carries out good and bad complementation, makes active material is obtained
The open-circuit voltage of battery can be reduced so that voltage platform is more steady, considerably increase the discharge capacity of battery, improve electric discharge
Efficiency；
What the 2nd, the conductive agent of lithium battery was conventional has the materials such as carbon fiber, CNT, and the particle diameter of carbon black is small, conducts distance
It is small, good conductivity, but easily reunite, it is difficult uniformly to mix with active material, carbon fiber and CNT have splendid
Axial one-dimensional electric ability, but their particle diameter it is big, it is necessary to conduction distance it is big；By carbon fiber, CNT respectively with
Carbon black mixes so that particle diameter is small, good conductivity carbon black enters in the aperture and space of carbon fiber and CNT, increased work
Property material contacts with each other, and improves the conductance of overall electrode, and can alleviate the stress that Volume Changes in charge and discharge process are brought,
Battery life is improved, one layer of gelatin is coated outside combined conductive agent, reduce dissolution of the electrolyte to conductive agent, further
Extend the service life of battery；
3rd, carbon nano-fiber is obtained by Electrospun and charing using acetic acid lignin and alkaline lignin, with preferable
Electric conductivity and pliability, and the additive of metal simple-substance is introduced in electro-spinning process, increase the electric conductivity of carbon fiber, enter one
Step increases the electric conductivity of conductive agent.
Further advantage of the invention, target and feature embody part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, to make those skilled in the art with reference to specification
Word can be implemented according to this.
It should be appreciated that it is used herein such as " have ", "comprising" and " including " term do not allot one or many
The presence or addition of individual other elements or its combination.
It should be noted that experimental technique described in following embodiments, unless otherwise specified, is conventional method, institute
Reagent and material are stated, unless otherwise specified, is commercially obtained.
<Embodiment 1>
A kind of lithium-iron disulfide anode material of lithium battery, it includes：
Positive active material, the positive active material is doped with the titanium oxide, 4% oxygen that mass percent is 2%
Change the ferrous disulfide of magnesium and 6% cupric oxide, the positive active material preparation method is specially：
A) ferrous disulfide that the separating-purifying from pyrite is obtained is divided into three equal parts, by the ferrous disulfide of three equal parts point
It is not put into the electric heating constant-temperature blowing drying box that temperature is 250 DEG C, 300 DEG C and 380 DEG C, taking-up is cooled to room temperature after preserving 24h,
First part of heat treatment ferrous disulfide, second part of heat treatment ferrous disulfide and the 3rd part of heat treatment ferrous disulfide are obtained, period is to three
Nitrogen is passed through in drying box；
B) first part of heat treatment ferrous disulfide is scattered in ball milling 2h in absolute ethyl alcohol, is then placed in 70 DEG C of vacuum drying
Dried in case, then drying object is scattered in deionized water, and be added thereto to slaine titanium tetrachloride solution and mixed with ammoniacal liquor
Close solution, be sufficiently stirred for filtering after 4h, collect the first filter residue and with absolute ethanol washing 1 time, by washing after the first filter residue put
Enter drying in 70 DEG C of vacuum drying chamber, then process 1h in 180 DEG C of high temperature inert gas, obtain the first cladding curing
Iron；Second part of heat treatment ferrous disulfide is scattered in ball milling 2h in acetone, is then placed in being dried in 70 DEG C of vacuum drying chamber, so
Drying object is scattered in deionized water afterwards, and is added thereto to slaine magnesium chloride solution and ammoniacal liquor mixed solution, fully stirred
Mix and filter after 4h, collect the second filter residue and simultaneously washed with acetone 1 time, by washing after the second filter residue be put into 70 DEG C of vacuum drying chamber
Middle drying, then processes 1h in 240 DEG C of high temperature inert gas, obtains the second cladding ferrous disulfide；Two are heat-treated by the 3rd part
Iron sulfide is scattered in ball milling 2h in dimethylformamide, is then placed in being dried in 170 DEG C of vacuum drying chamber, then by drying object
It is scattered in deionized water, and is added thereto to slaine copper-bath and ammoniacal liquor, filtered after being sufficiently stirred for 4h, collects the 3rd
Filter residue and with absolute ethanol washing 1 time, by washing after the 3rd filter residue be put into 170 DEG C of vacuum drying chamber in dry, Ran Hou
1h is processed in 300 DEG C of high temperature inert gas, the 3rd cladding ferrous disulfide is obtained；
C) ferrous disulfide, the second cladding ferrous disulfide and the 3rd cladding ferrous disulfide is coated by described first to put
Enter in the ball grinder of polytetrafluoroethylene (PTFE), be added thereto to the absolute ethyl alcohol ball milling of described first cladding, 3.2 times of weight of ferrous disulfide
, then be placed in the material in ball grinder in vacuum drying chamber by 3h, constant temperature 2h at 70 DEG C, and taking-up dried object is placed in grinding alms bowl and grinds
Clay into power, obtain final product.
Conductive agent, it is that weight ratio is 1:2:The compound that 3 carbon fibers, CNT and carbon black are formed；The conductive agent
Preparation method be specially：It is 2 that carbon black is divided into weight ratio:First part of 1 and second part, by first part of carbon black and CNT
It is placed in the ball grinder equipped with absolute ethyl alcohol, is taken out after ball milling 2h, be put into 100 DEG C of vacuum drying chamber and dry 10h, obtains first
Conductive material；Second part of carbon black and carbon fiber are put into the ball grinder equipped with absolute ethyl alcohol, are taken out after ball milling 2h, be put into 100
DEG C vacuum drying chamber in dry 10h, obtain the second conductive material；First conductive material and the second conductive material are poured into dissolved with bright
In the dimethyl sulphoxide solution of glue, filtered after high-speed stirred 40min, filtrate is washed 1 time with acetone and ethanol respectively, then
It is put into 100 DEG C of vacuum drying chamber and dries 4h, obtains final product the conductive agent；
The preparation method of the carbon fiber is：Count by weight, take 30 parts of acetic acid lignins, 20 parts of alkaline lignin
It is dissolved in respectively in 100 parts of acetic acid solution, configures the first solution and the second solution, to 0.01 part of addition in first solution
Metallic nickel, obtains the first spinning solution；0.01 part of metallic copper is added in second solution, the second spinning solution is obtained；By described first
Spinning solution and second spinning solution are placed in high-voltage electrostatic spinning device, carry out electrostatic spinning, obtain the first nanofiber and
Second nanofiber, the first nanofiber and the mixing of the second nanofiber are put into Muffle furnace and are pre-oxidized, then will be pre-
Mixture of nanofibers after oxidation is warming up to 700 DEG C under putting nitrogen protection, and heating rate is 100 DEG C/h, after carbonization treatment 1h
Room temperature is cooled to, crushing obtains final product the carbon fiber.
Binding agent, it includes that weight ratio is 3:1:1 butadiene-styrene rubber, sodium carboxymethylcellulose and polymethylacrylic acid；
Dispersant, the dispersant includes that weight ratio is 2:1 polyethylene glycol and polyvinyl alcohol；
Solvent, the solvent is 1-METHYLPYRROLIDONE.
In another technical scheme, described lithium-iron disulfide anode material of lithium battery, the positive active material,
The mass ratio 90.8 of the conductive agent, the binding agent and the dispersant:3.1:3.1:0.9, the solvent and the positive pole
The mass ratio of active material is 2.5:1.
<Embodiment 2>
A kind of lithium-iron disulfide anode material of lithium battery, it includes：
Positive active material, the positive active material is doped with the titanium oxide, 4% oxygen that mass percent is 2%
Change the ferrous disulfide of magnesium and 6% cupric oxide, the positive active material preparation method is specially：
A) ferrous disulfide that the separating-purifying from pyrite is obtained is divided into three equal parts, by the ferrous disulfide of three equal parts point
It is not put into the electric heating constant-temperature blowing drying box that temperature is 250 DEG C, 300 DEG C and 380 DEG C, taking-up is cooled to room temperature after preserving 24h,
First part of heat treatment ferrous disulfide, second part of heat treatment ferrous disulfide and the 3rd part of heat treatment ferrous disulfide are obtained, period is to three
Nitrogen is passed through in drying box；
B) first part of heat treatment ferrous disulfide is scattered in ball milling 4h in absolute ethyl alcohol, is then placed in 80 DEG C of vacuum drying
Dried in case, then drying object is scattered in deionized water, and be added thereto to slaine titanium tetrachloride solution and mixed with ammoniacal liquor
Close solution, be sufficiently stirred for filtering after 6h, collect the first filter residue and with absolute ethanol washing 3 times, by washing after the first filter residue put
Enter drying in 80 DEG C of vacuum drying chamber, then process 3h in 240 DEG C of high temperature inert gas, obtain the first cladding curing
Iron；Second part of heat treatment ferrous disulfide is scattered in ball milling 4h in acetone, is then placed in being dried in 80 DEG C of vacuum drying chamber, so
Drying object is scattered in deionized water afterwards, and is added thereto to slaine magnesium chloride solution and ammoniacal liquor mixed solution, fully stirred
Mix and filter after 6h, collect the second filter residue and simultaneously washed with acetone 3 times, by washing after the second filter residue be put into 80 DEG C of vacuum drying chamber
Middle drying, then processes 3h in 280 DEG C of high temperature inert gas, obtains the second cladding ferrous disulfide；Two are heat-treated by the 3rd part
Iron sulfide is scattered in ball milling 4h in dimethylformamide, is then placed in being dried in 220 DEG C of vacuum drying chamber, then by drying object
It is scattered in deionized water, and is added thereto to slaine copper-bath and ammoniacal liquor, filtered after being sufficiently stirred for 6h, collects the 3rd
Filter residue and with absolute ethanol washing 3 times, by washing after the 3rd filter residue be put into 220 DEG C of vacuum drying chamber in dry, Ran Hou
3h is processed in 340 DEG C of high temperature inert gas, the 3rd cladding ferrous disulfide is obtained；
C) ferrous disulfide, the second cladding ferrous disulfide and the 3rd cladding ferrous disulfide is coated by described first to put
Enter in the ball grinder of polytetrafluoroethylene (PTFE), be added thereto to the absolute ethyl alcohol ball milling of described first cladding, 3.2 times of weight of ferrous disulfide
, then be placed in the material in ball grinder in vacuum drying chamber by 5h, constant temperature 4h at 80 DEG C, and taking-up dried object is placed in grinding alms bowl and grinds
Clay into power, obtain final product.
Conductive agent, it is that weight ratio is 1:2:The compound that 3 carbon fibers, CNT and carbon black are formed；The conductive agent
Preparation method be specially：It is 2 that carbon black is divided into weight ratio:First part of 1 and second part, by first part of carbon black and CNT
It is placed in the ball grinder equipped with absolute ethyl alcohol, is taken out after ball milling 2h, be put into 100 DEG C of vacuum drying chamber and dry 10h, obtains first
Conductive material；Second part of carbon black and carbon fiber are put into the ball grinder equipped with absolute ethyl alcohol, are taken out after ball milling 2h, be put into 100
DEG C vacuum drying chamber in dry 10h, obtain the second conductive material；First conductive material and the second conductive material are poured into dissolved with bright
In the dimethyl sulphoxide solution of glue, filtered after high-speed stirred 60min, filtrate is washed 3 times with acetone and ethanol respectively, then
It is put into 100 DEG C of vacuum drying chamber and dries 6h, obtains final product the conductive agent；
The preparation method of the carbon fiber is：Count by weight, take 40 parts of acetic acid lignins, 28 parts of alkaline lignin
It is dissolved in respectively in 100 parts of acetic acid solution, configures the first solution and the second solution, to 0.03 part of addition in first solution
Metallic nickel, obtains the first spinning solution；0.03 part of metallic copper is added in second solution, the second spinning solution is obtained；By described first
Spinning solution and second spinning solution are placed in high-voltage electrostatic spinning device, carry out electrostatic spinning, obtain the first nanofiber and
Second nanofiber, the first nanofiber and the mixing of the second nanofiber are put into Muffle furnace and are pre-oxidized, then will be pre-
Mixture of nanofibers after oxidation is warming up to 700 DEG C under putting nitrogen protection, and heating rate is 100 DEG C/h, after carbonization treatment 1h
Room temperature is cooled to, crushing obtains final product the carbon fiber.
Binding agent, it includes that weight ratio is 3:1:1 butadiene-styrene rubber, sodium carboxymethylcellulose and polymethylacrylic acid；
Dispersant, the dispersant includes that weight ratio is 2:1 polyethylene glycol and polyvinyl alcohol；
Solvent, the solvent is 1-METHYLPYRROLIDONE.
In another technical scheme, described lithium-iron disulfide anode material of lithium battery, the positive active material,
The mass ratio 90.8 of the conductive agent, the binding agent and the dispersant:4.5:4.5:1.5, the solvent and the positive pole
The mass ratio of active material is 2.5:1.
<Embodiment 3>
A kind of lithium-iron disulfide anode material of lithium battery, it includes：
Positive active material, the positive active material is doped with the titanium oxide, 4% oxygen that mass percent is 2%
Change the ferrous disulfide of magnesium and 6% cupric oxide, the positive active material preparation method is specially：
A) ferrous disulfide that the separating-purifying from pyrite is obtained is divided into three equal parts, by the ferrous disulfide of three equal parts point
It is not put into the electric heating constant-temperature blowing drying box that temperature is 250 DEG C, 300 DEG C and 380 DEG C, taking-up is cooled to room temperature after preserving 24h,
First part of heat treatment ferrous disulfide, second part of heat treatment ferrous disulfide and the 3rd part of heat treatment ferrous disulfide are obtained, period is to three
Nitrogen is passed through in drying box；
B) first part of heat treatment ferrous disulfide is scattered in ball milling 3h in absolute ethyl alcohol, is then placed in 75 DEG C of vacuum drying
Dried in case, then drying object is scattered in deionized water, and be added thereto to slaine titanium tetrachloride solution and mixed with ammoniacal liquor
Close solution, be sufficiently stirred for filtering after 5h, collect the first filter residue and with absolute ethanol washing 2 times, by washing after the first filter residue put
Enter drying in 75 DEG C of vacuum drying chamber, then process 2h in 210 DEG C of high temperature inert gas, obtain the first cladding curing
Iron；Second part of heat treatment ferrous disulfide is scattered in ball milling 3h in acetone, is then placed in being dried in 75 DEG C of vacuum drying chamber, so
Drying object is scattered in deionized water afterwards, and is added thereto to slaine magnesium chloride solution and ammoniacal liquor mixed solution, fully stirred
Mix and filter after 5h, collect the second filter residue and simultaneously washed with acetone 2 times, by washing after the second filter residue be put into 75 DEG C of vacuum drying chamber
Middle drying, then processes 2h in 260 DEG C of high temperature inert gas, obtains the second cladding ferrous disulfide；Two are heat-treated by the 3rd part
Iron sulfide is scattered in ball milling 3h in dimethylformamide, is then placed in being dried in 195 DEG C of vacuum drying chamber, then by drying object
It is scattered in deionized water, and is added thereto to slaine copper-bath and ammoniacal liquor, filtered after being sufficiently stirred for 5h, collects the 3rd
Filter residue and with absolute ethanol washing 2 times, by washing after the 3rd filter residue be put into 195 DEG C of vacuum drying chamber in dry, Ran Hou
2h is processed in 320 DEG C of high temperature inert gas, the 3rd cladding ferrous disulfide is obtained；
C) ferrous disulfide, the second cladding ferrous disulfide and the 3rd cladding ferrous disulfide is coated by described first to put
Enter in the ball grinder of polytetrafluoroethylene (PTFE), be added thereto to the absolute ethyl alcohol ball milling of described first cladding, 3.2 times of weight of ferrous disulfide
, then be placed in the material in ball grinder in vacuum drying chamber by 4h, constant temperature 3h at 75 DEG C, and taking-up dried object is placed in grinding alms bowl and grinds
Clay into power, obtain final product.
Conductive agent, it is that weight ratio is 1:2:The compound that 3 carbon fibers, CNT and carbon black are formed；The conductive agent
Preparation method be specially：It is 2 that carbon black is divided into weight ratio:First part of 1 and second part, by first part of carbon black and CNT
It is placed in the ball grinder equipped with absolute ethyl alcohol, is taken out after ball milling 2h, be put into 100 DEG C of vacuum drying chamber and dry 10h, obtains first
Conductive material；Second part of carbon black and carbon fiber are put into the ball grinder equipped with absolute ethyl alcohol, are taken out after ball milling 2h, be put into 100
DEG C vacuum drying chamber in dry 10h, obtain the second conductive material；First conductive material and the second conductive material are poured into dissolved with bright
In the dimethyl sulphoxide solution of glue, filtered after high-speed stirred 50min, filtrate is washed 2 times with acetone and ethanol respectively, then
It is put into 100 DEG C of vacuum drying chamber and dries 5h, obtains final product the conductive agent；
The preparation method of the carbon fiber is：Count by weight, take 35 parts of acetic acid lignins, 24 parts of alkaline lignin
It is dissolved in respectively in 100 parts of acetic acid solution, configures the first solution and the second solution, to 0.02 part of addition in first solution
Metallic nickel, obtains the first spinning solution；0.02 part of metallic copper is added in second solution, the second spinning solution is obtained；By described first
Spinning solution and second spinning solution are placed in high-voltage electrostatic spinning device, carry out electrostatic spinning, obtain the first nanofiber and
Second nanofiber, the first nanofiber and the mixing of the second nanofiber are put into Muffle furnace and are pre-oxidized, then will be pre-
Mixture of nanofibers after oxidation is warming up to 700 DEG C under putting nitrogen protection, and heating rate is 100 DEG C/h, after carbonization treatment 1h
Room temperature is cooled to, crushing obtains final product the carbon fiber.
Binding agent, it includes that weight ratio is 3:1:1 butadiene-styrene rubber, sodium carboxymethylcellulose and polymethylacrylic acid；
Dispersant, the dispersant includes that weight ratio is 2:1 polyethylene glycol and polyvinyl alcohol；
Solvent, the solvent is 1-METHYLPYRROLIDONE.
In another technical scheme, described lithium-iron disulfide anode material of lithium battery, the positive active material,
The mass ratio 90.8 of the conductive agent, the binding agent and the dispersant:3.8:3.8:1.2, the solvent and the positive pole
The mass ratio of active material is 2.5:1.
<Embodiment 4>
A kind of lithium-iron disulfide anode material of lithium battery, the difference with embodiment 3 is that positive active material is modified
Ferrous disulfide, the positive active material is that doped with the titanium oxide that mass percent is 2%, the positive active material leads to
The ferrous disulfide for obtaining the separating-purifying from pyrite is crossed, according to heat treatment, the gold of the first equal portions ferrous disulfide in embodiment 3
Category oxidation cladding, dry, grind into powder are obtained, and remaining condition and parameter are with embodiment 3.
<Embodiment 5>
A kind of lithium-iron disulfide anode material of lithium battery, the difference with embodiment 3 is that positive active material is modified
Ferrous disulfide, the positive active material is that doped with the magnesia that mass percent is 4%, the positive active material leads to
The ferrous disulfide for obtaining the separating-purifying from pyrite is crossed, according to heat treatment, the gold of the second equal portions ferrous disulfide in embodiment 3
Category oxidation cladding, dry, grind into powder are obtained, and remaining condition and parameter are with embodiment 3.
<Embodiment 6>
A kind of lithium-iron disulfide anode material of lithium battery, the difference with embodiment 3 is that positive active material is modified
Ferrous disulfide, the positive active material is that doped with the cupric oxide that mass percent is 6%, the positive active material leads to
The ferrous disulfide for obtaining the separating-purifying from pyrite is crossed, according to heat treatment, the gold of three equal parts ferrous disulfide in embodiment 3
Category oxidation cladding, dry, grind into powder are obtained, and remaining condition and parameter are with embodiment 3.
<Embodiment 7>
A kind of lithium-iron disulfide anode material of lithium battery, the difference with embodiment 3 is, the conductive agent be carbon fiber,
CNT and carbon black pass through the compound being commonly mixed to form, and remaining condition and parameter are with embodiment 3.
<Embodiment 8>
A kind of lithium-iron disulfide anode material of lithium battery, the difference with embodiment 3 is that the carbon fiber is commercially available
Common carbon fibers, remaining condition and parameter are with embodiment 3.
<Comparative example 1>
The positive electrode provided using the embodiment of the present invention 3~8 is assembled into battery by identical method, and tests 6 kinds
Discharge capacity of the battery under 45mA constant-current discharges, tests 6 kinds of maximum compacted densities of positive electrode, as a result as shown in table 1：
| Numbering | Discharge capacity (Ah) | |
| Embodiment 3 | 2.67 | 3.89 |
| Embodiment 4 | 2.12 | 3.74 |
| Embodiment 5 | 2.09 | 3.73 |
| Embodiment 6 | 2.18 | 3.75 |
| Embodiment 7 | 2.35 | 3.25 |
| Embodiment 8 | 2.36 | 3.28 |
As shown in Table 1, the lithium-iron disulfide anode material of lithium battery that the embodiment of the present invention 3 is provided, has compared with embodiment 4~8
Discharge capacity and compacted density higher higher；Illustrate the present invention by the ferrous disulfide that obtains initial gross separation in batches, and
The heat treatment of different temperatures is carried out to the ferrous disulfide of different batches and different metal oxides are introduced, three kinds of crystalline phase knots are obtained
Structure, the granular size modified ferrous disulfide different with surface texture, and three kinds of modified ferrous disulfides are well mixed, it is obtained
The active material of ferrous disulfide as lithium-iron disulfide material, while be also added into combined conductive agent in positive electrode, energy
The compacted density and electric conductivity of enough positive electrodes significantly.
Number of devices described herein and treatment scale are for simplifying explanation of the invention.To application of the invention,
Modifications and variations will be readily apparent to persons skilled in the art.
Although embodiment of the present invention is disclosed as above, it is not restricted to listed in specification and implementation method
With, it can be applied to various suitable the field of the invention completely, for those skilled in the art, can be easily
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited
In specific details.
Claims (7)
1. a kind of lithium-iron disulfide anode material of lithium battery, it is characterised in that its positive-active for including modified ferrous disulfide
Material, the positive active material is doped with the titanium oxide, 4% magnesia and 6% cupric oxide that mass percent is 2%
Ferrous disulfide, the positive active material preparation method is specially：
A) ferrous disulfide that the separating-purifying from pyrite is obtained is divided into three equal parts, the ferrous disulfide of three equal parts is put respectively
In entering the electric heating constant-temperature blowing drying box that temperature is 250 DEG C, 300 DEG C and 380 DEG C, to preserve take out after 24h and be cooled to room temperature, obtain the
Portion heat treatment ferrous disulfide, second part of heat treatment ferrous disulfide and the 3rd part of heat treatment ferrous disulfide, period is to three dryings
Nitrogen is passed through in case；
B) first part of heat treatment ferrous disulfide is scattered in 2~4h of ball milling in absolute ethyl alcohol, is then placed in 70~80 DEG C of vacuum
Dried in drying box, then drying object is scattered in deionized water, and be added thereto to slaine titanium tetrachloride solution and ammonia
Water mixed solution, is sufficiently stirred for filtering after 4~6h, the first filter residue is collected and with absolute ethanol washing 1~3 time, after washing
First filter residue is dried in being put into 70~80 DEG C of vacuum drying chamber, then processes 1 in 180~240 DEG C of high temperature inert gas
~3h, obtains the first cladding ferrous disulfide；Second part of heat treatment ferrous disulfide is scattered in 2~4h of ball milling in acetone, is then placed in
Dried in 70~80 DEG C of vacuum drying chamber, then drying object is scattered in deionized water, and be added thereto to slaine chlorine
Change magnesium solution and ammoniacal liquor mixed solution, filtered after being sufficiently stirred for 4~6h, collect the second filter residue and washed with acetone 1~3 time, will
The second filter residue after washing is dried in being put into 70~80 DEG C of vacuum drying chamber, then in 240~280 DEG C of high temperature inert gas
1~3h of middle treatment, obtains the second cladding ferrous disulfide；3rd part of heat treatment ferrous disulfide is scattered in ball milling in dimethylformamide
2~4h, is then placed in being dried in 170~220 DEG C of vacuum drying chamber, and then drying object is scattered in deionized water, and to
Slaine copper-bath and ammoniacal liquor are wherein added, is filtered after being sufficiently stirred for 4~6h, collected the 3rd filter residue and washed with absolute ethyl alcohol
Wash 1~3 time, by washing after the 3rd filter residue be put into 170~220 DEG C of vacuum drying chamber and dry, then at 300~340 DEG C
High temperature inert gas in process 1~3h, obtain the 3rd cladding ferrous disulfide；
C) the described first cladding ferrous disulfide, the second cladding ferrous disulfide and the 3rd cladding ferrous disulfide are put into poly-
In the ball grinder of tetrafluoroethene, be added thereto to it is described first cladding 3.2 times of weight of ferrous disulfide absolute ethyl alcohol ball milling 3~
, then be placed in the material in ball grinder in vacuum drying chamber by 5h, 2~4h of constant temperature at 70~80 DEG C, and taking-up dried object is placed in and grinds
Grind into powder in mill alms bowl, obtains final product.
2. lithium-iron disulfide anode material of lithium battery as claimed in claim 1, it is characterised in that also including conductive agent, it is
Weight ratio is 1:2:The compound that 3 carbon fibers, CNT and carbon black are formed；The preparation method of the conductive agent is specially：Will
It is 2 that carbon black is divided into weight ratio:First part of 1 and second part, first part of carbon black and CNT are placed in equipped with absolute ethyl alcohol
In ball grinder, taken out after ball milling 2h, be put into 100 DEG C of vacuum drying chamber and dry 10h, obtain the first conductive material；By second part
Carbon black and carbon fiber are put into the ball grinder equipped with absolute ethyl alcohol, are taken out after ball milling 2h, are put into 100 DEG C of vacuum drying chamber and are done
Dry 10h, obtains the second conductive material；First conductive material and the second conductive material are poured into the dimethyl sulphoxide solution dissolved with gelatin
In, filtered after 40~60min of high-speed stirred, filtrate is washed 1~3 time with acetone and ethanol respectively, it is then placed in 100 DEG C
4~6h is dried in vacuum drying chamber, the conductive agent is obtained final product.
3. lithium-iron disulfide anode material of lithium battery as claimed in claim 2, it is characterised in that also including binding agent, its bag
It is 3 to include weight ratio:1:1 butadiene-styrene rubber, sodium carboxymethylcellulose and polymethylacrylic acid.
4. lithium-iron disulfide anode material of lithium battery as claimed in claim 3, it is characterised in that described also including dispersant
Dispersant includes that weight ratio is 2:1 polyethylene glycol and polyvinyl alcohol.
5. lithium-iron disulfide anode material of lithium battery as claimed in claim 4, it is characterised in that described molten also including solvent
Agent is 1-METHYLPYRROLIDONE.
6. lithium-iron disulfide anode material of lithium battery as claimed in claim 5, it is characterised in that the positive active material,
The mass ratio 90.8 of the conductive agent, the binding agent and the dispersant:3.1~4.5:3.1~4.5:0.9~1.5, it is described
Solvent is 2.5 with the mass ratio of the positive active material:1.
7. lithium-iron disulfide anode material of lithium battery as claimed in claim 6, it is characterised in that the preparation of the carbon fiber
Method is：Count by weight, take 30~40 parts of acetic acid lignins, 20~28 parts of alkaline lignin is dissolved in 100 parts respectively
In acetic acid solution, the first solution and the second solution are configured, to the metallic nickel that 0.01~0.03 part is added in first solution, obtained
First spinning solution；0.01~0.03 part of metallic copper is added in second solution, the second spinning solution is obtained；By first spinning
Liquid and second spinning solution are placed in high-voltage electrostatic spinning device, carry out electrostatic spinning, obtain the first nanofiber and second
Nanofiber, the first nanofiber and the mixing of the second nanofiber are put into Muffle furnace and are pre-oxidized, then will pre-oxidation
Mixture of nanofibers afterwards is warming up to 700 DEG C under putting nitrogen protection, and heating rate is 100 DEG C/h, is cooled down after carbonization treatment 1h
To room temperature, crushing obtains final product the carbon fiber.
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| CN1854229A (en) * | 2005-04-28 | 2006-11-01 | 深圳市比克电池有限公司 | Production of lithium ion battery cathode binder and cathode chip |
| CN1877887A (en) * | 2006-06-23 | 2006-12-13 | 清华大学 | Lithium-iron disulfide anode materials and method for preparing same |
| CN102751499A (en) * | 2012-06-30 | 2012-10-24 | 惠州亿纬锂能股份有限公司 | Lithium-ferrous disulfide battery and manufacturing method thereof |
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| CN1815779A (en) * | 2005-02-02 | 2006-08-09 | 深圳市比克电池有限公司 | Method for making lithium ion cell positive electrode sheet, positive-electrode sheet and lithium ion cell |
| CN1854229A (en) * | 2005-04-28 | 2006-11-01 | 深圳市比克电池有限公司 | Production of lithium ion battery cathode binder and cathode chip |
| CN1877887A (en) * | 2006-06-23 | 2006-12-13 | 清华大学 | Lithium-iron disulfide anode materials and method for preparing same |
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| CN111430714A (en) * | 2020-03-31 | 2020-07-17 | 东莞市天球实业有限公司 | Iron disulfide cathode material and preparation method thereof |
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