CN108682833A - A kind of iron phosphate lithium-based modified anode material preparation method - Google Patents
A kind of iron phosphate lithium-based modified anode material preparation method Download PDFInfo
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- CN108682833A CN108682833A CN201810600535.0A CN201810600535A CN108682833A CN 108682833 A CN108682833 A CN 108682833A CN 201810600535 A CN201810600535 A CN 201810600535A CN 108682833 A CN108682833 A CN 108682833A
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- zirconium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to technical field of lithium ion battery electrode, and in particular to a kind of iron phosphate lithium-based modified anode material preparation method includes the following steps：The compound in zirconium source is put into distilled water, and by ball mill pulverization process to grain size for after 2~12um, so, pass through the modification of graphene and carbon nanotube first, by the compound in zirconium source and allow zirconium and carbon bonding again, zirconium is introduced into graphene surface after heat treatment, obtain the carbon material of doping zirconium, the carbon material of doping zirconium is recycled to be modified LiFePO4, part zirconium is set to mix in LiFePO4, increase the electric conductivity between lithium iron phosphate particles, improve the compatibility between material surface and electrolyte, reduce resistance suffered when lithium ion mobility, and then improve the chemical property of battery at low ambient temperatures.
Description
Technical field：
The present invention relates to technical field of lithium ion battery electrode, and in particular to a kind of iron phosphate lithium-based modified positive material
Preparation method for material.
Background technology：
Lithium battery is one kind using lithium metal or lithium alloy as negative material, using the one-shot battery of non-aqueous electrolytic solution,
With lithium ion polymer battery it is different with rechargeable battery lithium ion battery.The inventor of lithium battery is Edison.By
It is very active in the chemical characteristic of lithium metal so that processing, preservation, the use of lithium metal, it is very high to environmental requirement.So
Lithium battery is not applied for a long time.With the development of twentieth century end microelectric technique, the equipment of miniaturization is increasing, right
Power supply proposes very high requirement.Lithium battery enters the large-scale practical stage therewith.Ferric phosphate lithium anode reacts：Electric discharge
When lithium ion be embedded in, lithium ion deintercalation when charging.When charging：When LiFePO4 → Li1-xFePO4+xLi++xe- discharges：Li1-
XFePO4+xLi++xe- → LiFePO4 cathode, negative material：Mostly use graphite.New research finds that titanate may be more preferable
Material.Negative reaction：Lithium ion is de- when electric discharge inserts, and lithium ion is inserted into when charging.When charging：XLi++xe-+6C → LixC6 is put
When electric：LixC6→xLi++xe-+6C.Ferric phosphate lithium cell has the characteristics that safety is good, energy density is higher, has become
Mainstream battery in power battery.However, under low temperature environment, institute is deviate from from positive electrode and migrated in the electrolytic solution to lithium ion
The resistance being subject to increases, and the charge-discharge performance and cycle performance of ferric phosphate lithium cell drastically reduce, and therefore, improves LiFePO4 electricity
Pond charge-discharge performance at low ambient temperatures and cycle performance are of great significance.
Currently, the synthetic method of LiFePO 4 material is largely divided into solid phase method and liquid phase method.Solid phase method mainly utilizes iron
Salt, lithium salts and phosphate realize the synthesis of LiFePO4 in high temperature sintering.Liquid phase method is by soluble ferric iron salt, lithium salts and phosphoric acid
Salt dissolves in a solvent, LiFePO4 or its presoma is made using ionic reaction, then finished product is made by high temperature sintering.Solid phase
Method reaction is easy, and raw material is easily processed, and yield is high, but raw material pattern is not easily controlled, product tap density and compacted density
It is low.For example, patent of invention CN101200289, CN1762798, CN101140985 etc. are to use process for solid phase synthesis route.
Some new synthetic methods, such as microwave process for synthesizing (CN101172597, CN101807692A), supersonic and co-deposition
(CN101800311A), it can sum up in the point that in solid-phase synthesis.And liquid phase method needs to carry out pre-processing using reaction kettle, together
When be also required to the processes such as dry, filtering, technics comparing is complicated.But product sphericity is generally preferable, tap density is higher, capacity
It is outstanding with high rate capability.Patent of invention CN101172599, CN101047242, CN101121509 are to use process above
Route.
The successful application of iron phosphate material is that its surface is coated with conductive carbon layer.Really a kind of lithium iron phosphate/carbon is multiple
Condensation material.Its chemical property could normally be played by only having coated the LiFePO 4 material of carbon.But general technique is added
Carbon due to quality it is loose, and in loose distribution between lithium iron phosphate particles, the accumulation for seriously reducing LiFePO 4 material is close
Degree.
Invention content：
The present invention overcomes the deficiencies of existing technologies, provide one kind can reduce lithium ion positive electrode surface abjection and it is embedding
Enter the polarization resistance of process, improve the high rate performance of material and the positive electrode of even compact.
The technical problems to be solved by the invention are realized using technical solution below：A kind of iron phosphate lithium-based modification is just
Pole material preparation method, includes the following steps：
(1) compound in zirconium source is put into distilled water, and is 2~12um by ball mill pulverization process to grain size
Afterwards, it is mixed 4~6 minutes at normal temperatures, obtains mixed liquor A；
(2) by mass ratio 2：1 graphene and carbon nanotube are put into distilled water, and are handled by ultrasonic preliminary crushing
Afterwards, it is mixed 4~6 minutes, is then heated up with the speed of 2~4 DEG C/min in the environment of inert gas shielding at normal temperatures
To 40~60 DEG C, then 4~6h is kept the temperature, then cooled to room temperature, obtains mixed liquid B；
(3) by mixed liquor A and mixed liquid B with volume ratio (1~2)：The mixing of 1 ratio obtains the carbon of zirconium doping
Material precursor, and the carbon materials material precursor that zirconium adulterates is dried by closed cycle spray drying machine, closed cycle spray
The inlet temperature and outlet temperature of mist drying machine are respectively 800~960 DEG C and 70~60 DEG C, the mist of closed cycle spray drying machine
The rotating speed for changing device is 24000~26000r/min, forms the carbon material of zirconium doping；
(3) LiFePO4 is crushed to 3~6um of grain size, and LiFePO4 is put into stirred tank, according to LiFePO4
With mass ratio=1 of distilled water：The ratio of (2~7) is slowly added distilled water, and adds coupling agent and conductive agent, quickly stirs
After 10~16min, the carbon material of the zirconium doping in step (3) is added in stirred tank, is stirred evenly, obtained modified intermediate
Body；
(4) will step (3) prepare modification intermediate be added atomizer in carry out spray drying treatment, should during be
It is blown into gaseous carbon source under protective gas effect, the gaseous carbon source is made to crack to form amorphous carbon in modified intermediate surface, it should
Agraphitic carbon is coated on the surface of modified intermediate and forms uniform clad, and the thickness of the clad is 2~6nm, i.e.,
For the iron phosphate lithium-based modified anode material.
Preferably, it is that the modification intermediate in the step (3) is put into atomizer in the application, in the step (4)
In, and be warming up to 500~700 DEG C in the state that protective gas is protected and made annealing treatment, then 24 are loaded by protective gas
~26% gaseous carbon source, 50~1000ml/min of gas flow rate, while atomizer is opened, protective gas will be atomized in atomizer
Tiny ingredient take in high temperature furnace, keep the temperature 1~12 hour, make the gaseous carbon source presoma surface crack to be formed it is amorphous
Carbon, it is 2~6nm clads, the as described phosphorus which, which is coated on the surface of modified intermediate and forms uniform thickness,
Sour iron lithium base modified anode material.
Preferably, in the application, the mass ratio of the compound in zirconium source and distilled water is (2~6) in the step (1)：50；
The mass ratio of the gross mass and distilled water of graphene and carbon nanotube is (4~4.8) in the step (2)：50.
Preferably, in the application, in step (3), the coupling agent is γ-mercaptopropyl trimethoxysilane, methyl tert-butyl
Base ketoximinosilanes or vinyltriethoxysilane, the conductive agent are sucrose or glucose, the coupling agent：It is conductive
Agent：The mass ratio of carbon material of zirconium doping is：(0.1~2：1~1.6：100).
Preferably, in the application, the protective gas described in step (5) is nitrogen or argon gas.
Preferably, in the application, the zirconium source is ZrO (NO3)2Or ZrOCl2。
Compared with prior art, the beneficial effects of the invention are as follows：
(1) in the application, first by the modification of graphene and carbon nanotube, then by the compound in zirconium source and zirconium is allowed
With carbon bonding, zirconium is introduced into graphene surface after heat treatment, obtains the carbon material of doping zirconium, recycles the carbon material of doping zirconium
LiFePO4 is modified, so that part zirconium is mixed in LiFePO4, the intrinsic conductivity of lithium iron phosphate particles can be improved, together
When, the zirconium for being scattered in carbon material surface contains more electron hole, has larger interaction force between LiFePO4,
Carbon material can be made to keep stablizing in charge and discharge process, be not easy to fall off from LiFePO4 surface, between increase lithium iron phosphate particles
Electric conductivity improves the compatibility between material surface and electrolyte, reduces resistance suffered when lithium ion mobility, and then improve
The chemical property of battery at low ambient temperatures；
(2) in the application, using the high conductivity of graphene and carbon nanotube, the graphene is multi-layer graphene, more
The inside of layer graphene is in 3 D stereo conductive network structure, and then promotes migration velocity of the lithium electronics in clad, and carbon is received
Mitron is inserted in the 3 D stereo conductive network, and the grain diameter formed after multi-layer graphene and carbon nanotube effect is
700nm~22um, which is to be mixed 4~6 minutes at normal temperatures, then with 2~4 in the environment of inert gas shielding
DEG C/speed of min is warming up to 40~60 DEG C, then keeps the temperature 4~6h, then cooled to room temperature, obtains mixed liquid B, such energy
Enough micro-bubbles further drained between multi-layer graphene and carbon nanotubes, form stable binder course, are conducive to preferably
Play the conductive characteristic of graphene and carbon nanotube；
(3) in the application, finally use is warming up to 500~700 DEG C in the state that protective gas is protected and carries out at annealing
Reason, the annealing can further promote the stability of modified intermediate, weaken graphene and nano-sized carbon in modified intermediate
Active force between pipe so that the positive electrode stability for preparing formation is strong, is then loaded into 24~26% by protective gas
Gaseous carbon source, 50~1000ml/min of gas flow rate, while opening atomizer, protective gas by be atomized in atomizer it is tiny at
Divide and take in high temperature furnace, keep the temperature 1~12 hour, the gaseous carbon source is made to crack to form amorphous carbon in modified intermediate surface,
The agraphitic carbon is coated on the surface of modified intermediate and forms uniform clad, obtains the anode material of lithium battery, should
For the thickness of clad between 0.3nm~30nm, main function is the stability for protecting lithium battery anode in formation process,
Since the cladding lamellar spacing is larger and thickness is smaller, clad is netted structure, will not stop the migration of lithium ion, simultaneously should
Clad can wrap up the active material of anode, that is to say, that this is wrapped on modified intermediate, to extend lithium electricity
Pond service life.
Specific implementation mode：
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be easy to understand, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1：
A kind of iron phosphate lithium-based modified anode material preparation method, includes the following steps：
(1) compound in zirconium source is put into distilled water, and is 2~12um by ball mill pulverization process to grain size
Afterwards, it is mixed 4~6 minutes at normal temperatures, obtains mixed liquor A；
(2) by mass ratio 2：1 graphene and carbon nanotube are put into distilled water, and are handled by ultrasonic preliminary crushing
Afterwards, it is mixed 4~6 minutes, is then heated up with the speed of 2~4 DEG C/min in the environment of inert gas shielding at normal temperatures
To 40~60 DEG C, then 4~6h is kept the temperature, then cooled to room temperature, obtains mixed liquid B；
(3) by mixed liquor A and mixed liquid B with volume ratio 1：The mixing of 1 ratio, before obtaining the carbon material of zirconium doping
Body is driven, and the carbon materials material precursor that zirconium adulterates is dried by closed cycle spray drying machine, closed cycle spray drying
The inlet temperature and outlet temperature of machine are respectively 800~960 DEG C and 70~60 DEG C, the atomizer of closed cycle spray drying machine
Rotating speed is 24000~26000r/min, forms the carbon material of zirconium doping；
(3) LiFePO4 is crushed to 3~6um of grain size, and LiFePO4 is put into stirred tank, according to LiFePO4
With mass ratio=1 of distilled water：The ratio of (2~7) is slowly added distilled water, and adds coupling agent and conductive agent, quickly stirs
After 10~16min, the carbon material of the zirconium doping in step (3) is added in stirred tank, is stirred evenly, obtained modified intermediate
Body；
(4) will step (3) prepare modification intermediate be added atomizer in carry out spray drying treatment, should during be
It is blown into gaseous carbon source under protective gas effect, the gaseous carbon source is made to crack to form amorphous carbon in modified intermediate surface, it should
Agraphitic carbon is coated on the surface of modified intermediate and forms uniform clad, and the thickness of the clad is 2~6nm, i.e.,
For the iron phosphate lithium-based modified anode material.
Be in the present embodiment, in the step (4) by the step (3) modification intermediate input atomizer in, and
It is warming up to 500~700 DEG C in the state that protective gas is protected to be made annealing treatment, 25% gas is then loaded by protective gas
State carbon source, 50~1000ml/min of gas flow rate, while atomizer is opened, the tiny ingredient that protective gas will be atomized in atomizer
It takes in high temperature furnace, keeps the temperature 1~12 hour, the gaseous carbon source is made to crack to form amorphous carbon on presoma surface, the nothing is fixed
Type carbon coating is on the surface of modified intermediate and to form uniform thickness be 2~6nm clads, as described iron phosphate lithium-based to change
Property positive electrode.
In the present embodiment, the mass ratio of the compound in zirconium source and distilled water is (2~6) in the step (1)：50；It is described
The mass ratio of the gross mass and distilled water of graphene and carbon nanotube is (4~4.8) in step (2)：50.
In the present embodiment, in step (3), the coupling agent is γ-mercaptopropyl trimethoxysilane, methyl isobutyl ketoxime
Base silane or vinyltriethoxysilane, the conductive agent are sucrose or glucose, the coupling agent：Conductive agent：Zirconium is mixed
The mass ratio of miscellaneous carbon material is：(0.1~2：1~1.6：100).
In the present embodiment, the protective gas described in step (5) is nitrogen, and the zirconium source is ZrO (NO3)2。
Embodiment 2
The present embodiment content and 1 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
Step (3) is by mixed liquor A and mixed liquid B with volume ratio 2：The mixing of 1 ratio obtains the carbon material forerunner of zirconium doping
Body, and the carbon materials material precursor that zirconium adulterates is dried by closed cycle spray drying machine, closed cycle spray drying machine
Inlet temperature and outlet temperature be respectively 800~960 DEG C and 70~60 DEG C, the atomizer of closed cycle spray drying machine turns
Speed is 24000~26000r/min, forms the carbon material of zirconium doping.
Embodiment 3
The present embodiment content and 1 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
Step (3) is by mixed liquor A and mixed liquid B with volume ratio 1.5：The mixing of 1 ratio obtains the carbon material forerunner of zirconium doping
Body, and the carbon materials material precursor that zirconium adulterates is dried by closed cycle spray drying machine, closed cycle spray drying machine
Inlet temperature and outlet temperature be respectively 800~960 DEG C and 70~60 DEG C, the atomizer of closed cycle spray drying machine turns
Speed is 24000~26000r/min, forms the carbon material of zirconium doping.
Embodiment 4
The present embodiment content and 3 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
It is to put into the modification intermediate in the step (3) in atomizer, and risen in the state that protective gas is protected in step (4)
Temperature is made annealing treatment to 500~700 DEG C, is then loaded into 24% gaseous carbon source by protective gas, and gas flow rate 50~
1000ml/min, while atomizer is opened, protective gas takes the tiny ingredient being atomized in atomizer in high temperature furnace to, heat preservation 1
~12 hours, the gaseous carbon source is made to crack to form amorphous carbon on presoma surface, which is coated on modified intermediate
The surface of body and formed uniform thickness be 2~6nm clads, the as described iron phosphate lithium-based modified anode material.
Embodiment 5
The present embodiment content and 3 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
It is to put into the modification intermediate in the step (3) in atomizer, and risen in the state that protective gas is protected in step (4)
Temperature is made annealing treatment to 500~700 DEG C, is then loaded into 26% gaseous carbon source by protective gas, and gas flow rate 50~
1000ml/min, while atomizer is opened, protective gas takes the tiny ingredient being atomized in atomizer in high temperature furnace to, heat preservation 1
~12 hours, the gaseous carbon source is made to crack to form amorphous carbon on presoma surface, which is coated on modified intermediate
The surface of body and formed uniform thickness be 2~6nm clads, the as described iron phosphate lithium-based modified anode material.
Comparative example 1
This comparative example content and 1 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
Step (3) is by mixed liquor A and mixed liquid B with volume ratio 0.5：The mixing of 1 ratio obtains the carbon material forerunner of zirconium doping
Body, and the carbon materials material precursor that zirconium adulterates is dried by closed cycle spray drying machine, closed cycle spray drying machine
Inlet temperature and outlet temperature be respectively 800~960 DEG C and 70~60 DEG C, the atomizer of closed cycle spray drying machine turns
Speed is 24000~26000r/min, forms the carbon material of zirconium doping.
Comparative example 2
This comparative example content and 1 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
Step (3) is by mixed liquor A and mixed liquid B with volume ratio 0.5：The mixing of 1 ratio obtains the carbon material forerunner of zirconium doping
Body, and the carbon materials material precursor that zirconium adulterates is dried by closed cycle spray drying machine, closed cycle spray drying machine
Inlet temperature and outlet temperature be respectively 800~960 DEG C and 70~60 DEG C, the atomizer of closed cycle spray drying machine turns
Speed is 24000~26000r/min, forms the carbon material of zirconium doping.
Comparative example 3
This comparative example content and 1 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
Step (3) is by mixed liquor A and mixed liquid B with volume ratio 3：The mixing of 1 ratio obtains the carbon material forerunner of zirconium doping
Body, and the carbon materials material precursor that zirconium adulterates is dried by closed cycle spray drying machine, closed cycle spray drying machine
Inlet temperature and outlet temperature be respectively 800~960 DEG C and 70~60 DEG C, the atomizer of closed cycle spray drying machine turns
Speed is 24000~26000r/min, forms the carbon material of zirconium doping.
Comparative example 4
This comparative example content and 3 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
It is to put into the modification intermediate in the step (3) in atomizer, and risen in the state that protective gas is protected in step (4)
Temperature is made annealing treatment to 500~700 DEG C, is then loaded into 22% gaseous carbon source by protective gas, and gas flow rate 50~
1000ml/min, while atomizer is opened, protective gas takes the tiny ingredient being atomized in atomizer in high temperature furnace to, heat preservation 1
~12 hours, the gaseous carbon source is made to crack to form amorphous carbon on presoma surface, which is coated on modified intermediate
The surface of body and formed uniform thickness be 2~6nm clads, the as described iron phosphate lithium-based modified anode material.
Comparative example 5
This comparative example content and 3 content of embodiment are essentially identical, and something in common no longer repeats, the difference is that：It is described
It is to put into the modification intermediate in the step (3) in atomizer, and risen in the state that protective gas is protected in step (4)
Temperature is made annealing treatment to 500~700 DEG C, is then loaded into 28% gaseous carbon source by protective gas, and gas flow rate 50~
1000ml/min, while atomizer is opened, protective gas takes the tiny ingredient being atomized in atomizer in high temperature furnace to, heat preservation 1
~12 hours, the gaseous carbon source is made to crack to form amorphous carbon on presoma surface, which is coated on modified intermediate
The surface of body and formed uniform thickness be 2~6nm clads, the as described iron phosphate lithium-based modified anode material.
Comparative example 6
With Chinese patent disclosed in application number " CN 201710610430.9 ", " a kind of positive electrode includes the positive electrode
Lithium ion battery and preparation method thereof " in embodiment 1 in positive electrode as a control group, table 1 is recorded in test result
In.
Performance test：
1, material electric conductivity
Sample in embodiment and comparative example is pressed into the thin slice that thickness is 1cm, square is coated on thin slice two sides
Conductive silver glue simultaneously bonds conductive filamentary silver, is connected on impedance analyzer (1260 type impedance analyzers of Solartron) and is surveyed
Examination, and test result is recorded in table 1.
2, electrochemical property test
The positive electrode obtained in above-described embodiment and comparative example is prepared into electrode slice：Kynoar is dissolved into first
It is configured to the glue that mass fraction is 7% in N-Methyl pyrrolidone, positive electrode is uniformly then ground into paste, by it
It is uniformly applied on aluminium foil and is placed under heat lamp and dry, be finally putting into 120 DEG C of vacuum drying ovens and toast 5h, be cooled to room temperature and incite somebody to action
Aluminium foil cuts into the electrode slice of 8 × 8mm2；
Using lithium piece as cathode, polypropylene screen is diaphragm, sub- using lithium hexafluoro phosphate as solute and ethylene carbonate and carbonic acid
Ethyl ester mixing is electrolyte as the solution of solvent, button cell is assembled into the glove box of argon atmosphere, using filling
Discharge tester button type battery carries out constant current charge-discharge test under room temperature, and test result is recorded in table 1, makes
With cryostat (the high prosperous detection device GX-3000-80L high/low temperatures insulating box of Dongguan City) setting and meet the low of test needs
Warm condition.
Table 1
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (6)
1. a kind of iron phosphate lithium-based modified anode material preparation method, which is characterized in that include the following steps：
(1) compound in zirconium source is put into distilled water, and by ball mill pulverization process to grain size be 2~12um after,
It is mixed 4~6 minutes under room temperature, obtains mixed liquor A；
(2) by mass ratio 2：1 graphene and carbon nanotube are put into distilled water, and by ultrasonic preliminary crushing handle after,
It is mixed 4~6 minutes under room temperature, then 40 are warming up to the speed of 2~4 DEG C/min in the environment of inert gas shielding~
60 DEG C, then 4~6h is kept the temperature, then cooled to room temperature, obtains mixed liquid B；
(3) by mixed liquor A and mixed liquid B with volume ratio (1~2)：The mixing of 1 ratio obtains the carbon material of zirconium doping
Presoma, and the carbon materials material precursor that zirconium adulterates is dried by closed cycle spray drying machine, closed cycle spray is dry
The inlet temperature and outlet temperature of dry machine are respectively 800~960 DEG C and 70~60 DEG C, the atomizer of closed cycle spray drying machine
Rotating speed be 24000~26000r/min, formed zirconium doping carbon material；
(3) LiFePO4 is crushed to 3~6um of grain size, and LiFePO4 is put into stirred tank, according to LiFePO4 and steaming
Mass ratio=1 of distilled water：The ratio of (2~7) is slowly added distilled water, and adds coupling agent and conductive agent, quickly stir 10~
After 16min, the carbon material of the zirconium doping in step (3) is added in stirred tank, is stirred evenly, modified intermediate is obtained；
(4) modification intermediate prepared by step (3) is added in atomizer and carries out spray drying treatment, should be in the process to protect
It is blown into gaseous carbon source under gas effect, makes the gaseous carbon source crack to form amorphous carbon in modified intermediate surface, the nothing is fixed
Type carbon coating is on the surface of modified intermediate and forms uniform clad, and the thickness of the clad is 2~6nm, as institute
State iron phosphate lithium-based modified anode material.
2. iron phosphate lithium-based modified anode material preparation method according to claim 1, which is characterized in that the step
(4) it is to put into the modification intermediate in the step (3) in atomizer, and be warming up in the state that protective gas is protected in
500~700 DEG C are made annealing treatment, then by protective gas be loaded into 24~26% gaseous carbon source, gas flow rate 50~
1000ml/min, while atomizer is opened, protective gas takes the tiny ingredient being atomized in atomizer in high temperature furnace to, heat preservation 1
~12 hours, the gaseous carbon source is made to crack to form amorphous carbon on presoma surface, which is coated on modified intermediate
The surface of body and formed uniform thickness be 2~6nm clads, the as described iron phosphate lithium-based modified anode material.
3. iron phosphate lithium-based modified anode material preparation method according to claim 1, which is characterized in that the step
(1) mass ratio of the compound in zirconium source and distilled water is (2~6) in：50；Graphene and carbon nanotube in the step (2)
Gross mass and the mass ratio of distilled water are (4~4.8)：50.
4. the lithium battery according to claim 1 preparation method of modified phosphate iron lithium anode material, which is characterized in that step
Suddenly in (3), the coupling agent is three ethoxy of γ-mercaptopropyl trimethoxysilane, methyl isobutyl ketoxime base silane or vinyl
Base silane, the conductive agent are sucrose or glucose, the coupling agent：Conductive agent：The mass ratio of carbon material of zirconium doping is：
(0.1~2：1~1.6：100).
5. iron phosphate lithium-based modified anode material preparation method according to claim 1, which is characterized in that in step (5)
The protective gas is nitrogen or argon gas.
6. iron phosphate lithium-based modified anode material preparation method according to claim 1, which is characterized in that the zirconium source is
ZrO(NO3)2Or ZrOCl2。
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