CN104752716B - Lithium iron phosphate and its preparation method and use - Google Patents
Lithium iron phosphate and its preparation method and use Download PDFInfo
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- CN104752716B CN104752716B CN201310739960.5A CN201310739960A CN104752716B CN 104752716 B CN104752716 B CN 104752716B CN 201310739960 A CN201310739960 A CN 201310739960A CN 104752716 B CN104752716 B CN 104752716B
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a preparation method of lithium iron phosphate, the lithium iron phosphate and a use of the lithium iron phosphate as a positive pole active material. The preparation method of the lithium iron phosphate is characterized in that a water-soluble divalent iron source, a water-soluble phosphor source and a water-soluble lithium source contact and undergo a reaction, the water-soluble phosphor source is phosphoric acid and/or water-soluble phosphate, the reaction metohd comprises adjusting pH of the contacting product to more than 7, fast heating the alkaline product to a temperature of 80-240 DEG C, carrying out a first reaction process, cooling the product obtained by the first reaction to 20-50 DEG C, adjusting pH of the product to less than 7, fast heating the acidic product to a temperature of 80-240 DEG C, and carrying out a second reaction process, and the fast heating process has a heating rate greater than or equal to 10 DEG/s. The lithium iron phosphate has small particle sizes and excellent electrochemical performances.
Description
Technical field
The present invention relates to a kind of preparation method of LiFePO4, the LiFePO4 being prepared by the method and described phosphorus
Sour iron lithium is as the application of positive electrode active materials.
Background technology
Lithium ion battery has been widely used for mobile communication, notebook computer, takes the photograph as the electrochmical power source of height ratio capacity
The fields such as camera, camera, portable instrument, are also that the electric automobile studied energetically of various countries, the first-selection of space power system are joined
Set power supply, becomes the first-selection of fungible energy source.
LiFePO4（LiFePO4）It is the study hotspot of active substance of lithium ion battery anode.Primary Study shows,
LiFePO4Concentrate LiCoO2、LiNiO2、LiMnO4Deng the respective advantage of material, such as without precious metal, raw material be cheap, resource
Abundant, operating voltage is moderate（3.4V）, platform identity is good, voltage is steady, theoretical capacity is big（170mAh/g）, Stability Analysis of Structures, peace
Full excellent performance（Oxygen and phosphorus, with strong covalent bond strong bonded, make material be difficult to analysis oxygen solution）, high-temperature behavior and good cycle, fill
Volume-diminished and bulk effect during carbon negative pole material cooperation is good and most of electrolyte system compatibility is good, storage characteristics when electric
Can be good and nontoxic etc., can be used as real green energy resource.
Traditional hydro-thermal method synthesizing iron lithium phosphate is generally one-shot forming granulation, i.e. the presoma of synthesis only need to be through too high
A pressure temperature reaction of reactor synthesis, will not be re-introduced into other variables to change its physico-chemical property in temperature-rise period.However,
Although the process using the method is simple, because the essence of hydro-thermal method synthesizing iron lithium phosphate is the forerunner of indissoluble at normal temperatures
Body can be partly dissolved at high temperature, be completely dissolved or in-situ crystallization is thus form new thing phase, and presoma is in the mistake heating up
Phase transition, thing phased soln and thing phase nucleation itself also can occur in journey, therefore the physico-chemical property of presoma is required to compare
High.If presoma thing is mutually too stable or is not readily converted into LiFePO4 at high temperature, its formation condition will be harsher, this
Sample notably makes part presoma cannot be converted into LiFePO4, and the conversion ratio of the material of LiFePO4 also not only can be made to reduce,
And the LiFePO4 non-fully converting mutually also can increase, thus leading to chemical property such as capacity, compacted density, cycle performance
To be a greater impact Deng all.
Meanwhile, the method for traditional hydro-thermal method synthesizing iron lithium phosphate typically has two kinds.A kind of is first to prepare phosphoric acid under normal temperature
Lithium, then adds copperas solution, then rises high-temperature and to synthesis temperature and reacts, then again product is lowered the temperature,
Washing, filtration can get LiFePO4.The particle diameter of the LiFePO4 synthesizing under this condition is less, is concentrated mainly on sub-micro
Rice, and under the pressure of 4MPa, the compacted density of this LiFePO4 maintains essentially between 1.9-2.0g/cc, but such
The chemical property of the LiFePO4 arriving is poor.After another kind is for mixing phosphoric acid with ferrous sulfate at normal temperatures completely, then will
Lithium hydroxide solution is mixed, is warming up to synthesis temperature and reacts after reaction completely, then again product is lowered the temperature,
Washing, filtration can get LiFePO4.The particle diameter of the LiFePO4 synthesizing under this condition is larger, generally higher than 3um, and
Under the pressure of 4MPa, the compacted density of this LiFePO4 maintains essentially between 2.0-2.1g/cc.Additionally, existing hydro-thermal method
Prepare the pH value that LiFePO4 adopted and be single pH value.The charging of the LiFePO4 being prepared using existing hydro-thermal method
Capacity maintains essentially in 155-160mAh/g, and discharge capacity maintains essentially in 153-158mAh/g.
Content of the invention
Present invention aim to address can not being obtained using existing method, particle diameter is little and electrochemical performance simultaneously
LiFePO4 defect, and provide a kind of preparation method of new LiFePO4, the LiFePO4 being prepared by the method
And described LiFePO4 is as the application of positive electrode active materials.It is obtained in that particle diameter is little and chemical property is excellent using the method
Different LiFePO4.
The invention provides a kind of preparation method of LiFePO4, the method is included watersoluble divalent source of iron, water solubility
Phosphorus source and water-soluble lithium source contact and react, and described water solubility phosphorus source is phosphoric acid and/or water-soluble phosphate, wherein, described
The mode of reaction includes adjusting the pH value of product of contact to alkalescence, and alkaline product is rapidly heated to 80-240 DEG C carries out the
Then the product of the described first reaction is down to 20-50 DEG C and is adjusted its pH value to acidity by one reaction, then acid product is fast
Speed is warming up to 80-240 DEG C and carries out the second reaction；Described being rapidly heated refers to that heating rate is not less than 10 DEG C/s.
Present invention also offers the LiFePO4 being prepared by said method.
Additionally, present invention also offers described LiFePO4 as positive electrode active materials application.
The present inventor finds through further investigation, and existing hydro-thermal method is prepared LiFePO4 and typically will be reacted former
Material（As watersoluble divalent source of iron, water-soluble phosphorus source and water-soluble lithium source）Mix to generate presoma at normal temperatures, then will
Temperature is slowly increased to synthesis temperature reaction, and the pH value being adopted during the course of the reaction is single pH value, so obtains
LiFePO4 chemical property generally poor.Speculate its reason it may be possible to due to：On the one hand, when by described presoma
When temperature rises to 45-80 DEG C, described presoma easily generates the intermediate product being difficult to convert into LiFePO4 at high temperature, so
The purity of LiFePO4 finally giving can be led to relatively low；On the other hand, carry out reaction under single pH value and have lacking as follows
Fall into：In acid condition, due to there being part thing phase such as Fe in presoma3(PO4)2.8H2The degree of crystallinity of O can increase, solubility and work
Property can reduce, and final LiFePO 4 material performance will decline；In the basic conditions although the degree of crystallinity of thing phase can be reduced,
The increase but other thing phase such as alkali formula ferrous phosphates, ferrous hydroxide thing are met, therefore, still can reduce final LiFePO4 material
The performance of material；In neutral conditions, the particle diameter of the LiFePO4 obtaining is larger and skewness, thus it will greatly be suppressed
Chemical property.
And the present invention can control the nucleation and crystallization of LiFePO4 by the secondary regulation being rapidly heated and combining pH value, and
And then obtain that particle diameter is little and the LiFePO4 of electrochemical performance.Speculate its reason it may be possible to due to：On the one hand, the present invention
Using the temperature of described alkaline product and acid product being rapidly increased to more than 80 DEG C by the way of being rapidly heated, can effectively keep away
Exempt from the thing of presoma opposite non-controlling direction in temperature-rise period to change, and then reduce the generation of unfavorable thing phase；On the other hand, exist
The degree of crystallinity of presoma can be reduced, at a temperature of Hydrothermal Synthesiss, the nucleation rate of LiFePO4 will be substantially big under alkalescence condition
In the speed of growth, the lithium iron phosphate particles now being formed are mainly Nano grade, additionally, still have in the basic conditions more in
Between thing be not mutually fully converted to LiFePO4, and unconverted LiFePO4 basic bit is in particle surface, consequently facilitating subsequently
Participate in reaction further；And acid condition is the suitable synthesis pH value of LiFePO4, enable to unconverted in the basic conditions
Intermediate phase for LiFePO4 is substantially transitioned to LiFePO4, thus improving the purity of the LiFePO4 obtaining.
A preferred embodiment of the invention, when the pH value of described alkaline product is 7.5-14, described acid product
When the pH value of thing is 4-6.5, it is obtained in that the more preferable LiFePO4 of chemical property.
According to another kind of preferred embodiment of the present invention, when the preparation method of described LiFePO4 also includes living in surface
Property agent and watersoluble divalent source of iron, when being contacted and reacted together with water-soluble phosphorus source and water-soluble lithium source additionally it is possible to increase
The volume energy density of the LiFePO4 obtaining, thus be more beneficial for obtaining the less battery of volume.Speculate its reason it may be possible to
Due to：The ferric lithium phosphate precursor particle that the addition of surfactant enables to is coated by described surfactant, thus
Prevent growth on described granular precursor for the LiFePO4, the growth course of described LiFePO4 is changed into dissolution-crystallization machine
System, i.e. described presoma slowly releases ion, then between ion, fast reaction generates LiFePO4 such that it is able to carry again
The controllability of high described LiFePO4 preparation process simultaneously improves its volume energy density.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of specification, with following tool
Body embodiment is used for explaining the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the stereoscan photograph of the LiFePO4 of embodiment 1 preparation, and multiplication factor is 50000 times；
Fig. 2 is the stereoscan photograph of the LiFePO4 of embodiment 1 preparation, and multiplication factor is 20000 times；
Fig. 3 is the stereoscan photograph of the LiFePO4 of embodiment 4 preparation, and multiplication factor is 50000 times；
Fig. 4 is the stereoscan photograph of the LiFePO4 of embodiment 4 preparation, and multiplication factor is 20000 times；
Fig. 5 is the stereoscan photograph of the LiFePO4 of comparative example 1 preparation, and multiplication factor is 20000 times；
Fig. 6 is the stereoscan photograph of the LiFePO4 of comparative example 1 preparation, and multiplication factor is 50000 times；
Fig. 7 is the stereoscan photograph of the LiFePO4 of comparative example 2 preparation, and multiplication factor is 50000 times；
Fig. 8 is the stereoscan photograph of the LiFePO4 of comparative example 2 preparation, and multiplication factor is 20000 times.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides the preparation method of LiFePO4 is included watersoluble divalent source of iron, water-soluble phosphorus source and water-soluble
Property lithium source contact and react, described water solubility phosphorus source be phosphoric acid and/or water-soluble phosphate, wherein, the mode bag of described reaction
Include and adjust the pH value of product of contact to alkalescence, and alkaline product is rapidly heated to 80-240 DEG C carries out the first reaction, then
The product of the described first reaction is down to 20-50 DEG C and is adjusted its pH value to acidity, then acid product is rapidly heated to 80-
240 DEG C carry out the second reaction；Described being rapidly heated refers to that heating rate is not less than 10 DEG C/s.
According to the present invention, although as long as the described heating rate being rapidly heated is controlled being not less than 10 DEG C/s,
As a rule, heating rate raising that is more fast more being conducive to LiFePO4 purity, but this simultaneously also can to heating mode and
Condition proposes harsher requirement, and therefore, combined factors from every side consider, by described alkaline product be rapidly heated with by institute
State the heating rate that acid product is rapidly heated can identical it is also possible to different, and be each independently 30-250 DEG C/s.
In accordance with the present invention it is preferred that, the pH value of described alkaline product is 7.5-14, and the pH value of described acid product is 4-
6.5, i.e. adjust the pH value of described product of contact to 7.5-14, the pH value of the product of the described first reaction is adjusted to 4-
6.5, so can obtain the more excellent LiFePO4 of chemical property.The pH value of described product of contact is controlled alkaline, excellent
Selected control system 7.5-14 mode can to reaction system in add alkaline matter.Described alkaline matter for example can for ammoniacal liquor,
One or more of potassium hydroxide, NaOH, lithium hydroxide, sodium carbonate and potassium carbonate, particularly preferably lithium hydroxide, this
Sample is it can be avoided that the introducing of impurity.The pH value of described first product is controlled in mode that is acid, being preferably controlled in 4-6.5
Acidic materials can be added in reaction system.Described acidic materials can be for example in phosphoric acid, sulfuric acid, nitric acid and hydrochloric acid
Plant or multiple.Described acidic materials are used generally in the form of its aqueous solution, and during use, its concentration can be 0.01-1mol/L.
The consumption of described alkaline matter and acidic materials is defined in above range by controlling pH value, and therefore not to repeat here.Additionally, working as institute
State alkaline matter to be lithium hydroxide and/or described acidic materials when being phosphoric acid, for adjusting the lithium hydroxide of pH value of reaction system
It is not counted in the consumption of reaction raw materials with the consumption of phosphoric acid.
The present invention to by described alkaline product be rapidly heated to 80-240 DEG C and by described acid product be rapidly heated to
80-240 DEG C of mode is not particularly limited, for example, it is possible to described alkaline product or acid product are dropped to temperature be
In 80-240 DEG C of water, so by the heat exchange between described alkaline product or acid product and water, alkalescence can be produced
The temperature of thing or acid product raises rapidly.As a rule, the boiling point of water is 100 DEG C at ambient pressure, therefore, in order to obtain temperature
The water of higher such as 240 DEG C of degree, can increase pressure to improve the boiling point of water.Additionally, on the basis of the described alkaline product of 1L,
Described temperature is the consumption of 80-240 DEG C of water can be 1-10L；On the basis of the described acid product of 1L, described temperature is
The consumption of 80-240 DEG C of water can be 1-10L.Described alkaline product and the drop rate of acid product can identical it is also possible to
Difference, and by the temperature of 1L for 80-240 DEG C of water on the basis of, the drop rate of described alkaline product and acid product is permissible
It is each independently 1-100mL/s, preferably 1-10mL/s.It should be noted that when using above-mentioned by alkaline product with acidity
Product drops to when realizing being rapidly heated in the water that temperature is 80-240 DEG C, may regard as described alkaline product and acid product
Temperature is risen to 80-240 DEG C in the time of 1 second by thing, and heating rate is（Final temperature-initial temperature）÷1.For example, in embodiment 1
In, it is in 130 DEG C of deionized water that the alkaline product that temperature is 45 DEG C instills temperature, and the temperature in reactor is in 125-135
Fluctuate between DEG C, then heating rate is（125-45）1 DEG C/s of ÷ is extremely（135-45）1 DEG C/s of ÷, as 80-90 DEG C/s.
The present invention is not particularly limited to the condition of the described first reaction, and for example, the condition of described first reaction includes：
Reaction temperature can be 80-240 DEG C, preferably 120-240 DEG C；Reaction pressure can be 0-5MPa, preferably 0-2.5MPa；Instead
Can be 0.5-5 hour, preferably 0.5-2.5 hour between seasonable.
The present invention is not particularly limited to the condition of the described second reaction, and for example, the condition of described second reaction includes：
Reaction temperature can be 80-240 DEG C, preferably 120-240 DEG C；Reaction pressure can be 0-5MPa, preferably 0-2.5MPa；Instead
Can be 2-14 hour, preferably 2-5 hour between seasonable.
In the present invention, described pressure refers both to gauge pressure.
It should be noted that the temperature that the temperature being quickly ramped up to described alkaline product is reacted with described first may not
Same, at this point it is possible to first described alkaline product is quickly ramped up to predetermined temperature, then slowly adjust again to the temperature of the first reaction；
The temperature of the temperature that described acid product is quickly ramped up to and the described second reaction be likely to different it is also possible to first by described acidity
Product is quickly ramped up to predetermined temperature, then slowly adjusts to the temperature of the second reaction again.
Additionally, in order to avoid in the air oxygen to the oxidation of ferrous ion in material it is preferable that described first reaction
Carry out in an inert atmosphere with the second reaction.Wherein, the mode keeping inert atmosphere can be that inert gas is passed through reactant
To replace the non-inert gas in described reaction system in system, then again the reaction system after gas displacement is sealed.Described
Inert gas can be nitrogen and/or helium.
The present invention does not especially limit to the consumption of described watersoluble divalent source of iron, water-soluble phosphorus source and water-soluble lithium source
Fixed, for example, the consumption of the consumption of described watersoluble divalent source of iron, the consumption of described water solubility phosphorus source and described water solubility lithium source
So that to product of contact in Fe2+、PO4 3-With Li+Mol ratio be（0.95-1.05）:（0.95-1.05）:3, preferably
（0.97-1.03）:（0.97-1.03）:3.
Described watersoluble divalent source of iron can be the existing various compounds containing ferrous ion that can be dissolved in water, its
Instantiation includes but is not limited to：Frerrous chloride, ferrous bromide, ferrous fluosilicate, ferrous nitrate, ferrous perchlorate, sulfuric acid are sub-
One or more of iron and ferrous acetate.Additionally, described ferrous sulfate can be without the crystallization water it is also possible to carry crystallization
Water, is specifically as follows one or more of anhydrous slufuric acid ferrous iron, ferrous sulfate monohydrate, ferrous sulfate heptahydrate etc..
The example of described water-soluble phosphate includes but is not limited to：Lithium dihydrogen phosphate, sodium phosphate, ammonium dihydrogen phosphate, phosphoric acid
One or more of hydrogen two ammonium and potassium phosphate.
Described water solubility lithium source can be the existing various compounds containing lithium that can be dissolved in water, and its instantiation includes
But it is not limited to：Lithium hydroxide, lithium acetate, lithium benzoate, lithium bromate, lithium bromide, lithium chlorate, lithium chloride, lithium fluoride, fluosilicic acid
One or more of lithium, lithium formate, lithium iodide, lithium nitrate, lithium perchlorate, lithium tartrate and lithium carbonate, particularly preferably hydrogen
Lithia.Additionally, described lithium hydroxide can be without the crystallization water it is also possible to carry the crystallization water（As monohydrate lithium hydroxide）.
It should be noted that when the raw material preparing described LiFePO4 contains lithium dihydrogen phosphate, described lithium dihydrogen phosphate
Regard as described water-soluble phosphate add, and by the consumption of described lithium dihydrogen phosphate count simultaneously water-soluble phosphate and
In the consumption of water-soluble lithium source, i.e. contained lithium in described lithium dihydrogen phosphate need to be deducted when adding other lithium source.
According to the present invention, the preparation method of described LiFePO4 also include by surfactant and watersoluble divalent source of iron,
Water-soluble phosphorus source and water-soluble lithium source are contacted together and are reacted, and so can increase the volume energy of the LiFePO4 obtaining
Metric density, thus be more beneficial for obtaining the less battery of volume.Normally, the consumption of described surfactant and described water solubility
The mol ratio of the consumption of lithium source can be（0.0001-0.01）:1, preferably（0.0002-0.008）:1.Additionally, described surface
The example of activating agent includes but is not limited to：Cetyl trimethylammonium bromide, laurate quaternary ammonium salt, cetyl benzenesulfonic acid
One of sodium, citric acid, polyethylene glycol, sodium hexadecyl sulfate, Gemini quaternary ammonium salt and DGE carboxylate
Or it is multiple.
The present invention is not particularly limited to the mode of described contact, for example, it is possible to first by watersoluble divalent molysite, water-soluble
Property phosphorus source and the surfactant that selectively contains soluble in water, obtain water solution A, and will be soluble in water for water-soluble lithium source,
Obtain aqueous solution B, then under agitation, described aqueous solution B is slowly added dropwise to described water solution A, after charging finishes
Continue stirring to mix to temperature constant；Or under agitation, described water solution A is slowly added dropwise to described aqueous solution B,
Charging continues stirring after finishing and mixes to temperature constant；Or under agitation, by described water solution A with aqueous solution B simultaneously
Drop in same reactor, charging continues stirring after finishing and mixes to temperature constant.
According to the present invention, the preparation method of described iron manganese phosphate for lithium also includes filtering, wash and do described product
Dry.Wherein, described washing can first be washed with deionized 1-3 time, then with absolute ethanol washing 1-3 time.
In accordance with the present invention it is preferred that, the preparation method of described LiFePO4 also include by described second product with have
Machine carbon source is mixed and is spray-dried, then the Spray dried products obtaining are carried out roasting, so can improve further
The chemical property of the LiFePO4 arriving.
The present invention is not particularly limited to the species of described organic carbon source and consumption.As a rule, described organic carbon source
Can for existing various can below 500 DEG C carbonization organic matter, its instantiation includes but is not limited to：Glucose, sugarcane
One or more of sugar, lactose, maltose, phenolic resin and epoxy resin.Additionally, the consumption of described organic carbon source should root
Amount according to product is selected, for example, in terms of the dry weight of described second product of 100 weight portions, described organic carbon
The consumption in source can be 2-20 weight portion, preferably 5-15 weight portion.
According to the present invention, the concrete operation method of described spray drying and condition are known to the skilled person.Specifically
Ground, will be added in atomizer high-speed rotation to realize spray by the slurry that described second product is made into organic carbon source and water
Mist is dried.The temperature of described spray drying can be 60-150 DEG C, preferably 80-120 DEG C.It should be noted that described second
Product can be through dried product or undried product.When described second product be through
When crossing the product being dried, the second product of solid, organic carbon source and additional water can be mixed to obtain described slurry
Body；When described second product is undried product, can by itself contain the product of certain water directly with
Organic carbon source mixing obtaining described slurry, if it is also possible to additionally add certain during contained in product water shortage
The water of amount.Additionally, the amount of water can be the conventional selection of this area in described slurry, as well known to those skilled in the art to this,
This does not repeat.
The present invention is not particularly limited to the condition of described roasting, if can by described organic carbon source carbonization,
For example, the condition of described roasting includes sintering temperature can be 600-750 DEG C, and roasting time can be 3-12 hour.Additionally, institute
State roasting generally to carry out in an inert atmosphere.
Present invention also offers the LiFePO4 being prepared by said method.
Additionally, present invention also offers described LiFePO4 as positive electrode active materials application.
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example, SEM（SEM）For Japanese Shimadzu Corporation（Shimadzu）Produce
SSX-550 type SEM, test voltage be 5KV.X-ray diffractometer is the general analysis in Beijing all purpose instrument Limited Liability
The XD-2 type X-ray diffractometer that company produces, wherein, test condition includes：Pipe is pressed as 200mA, and electric current is 200mA, and step-length is
1 °, test angle is 10 ° -90 °.
Embodiment 1
This embodiment is used for LiFePO4 that the present invention provides and preparation method thereof is described.
By 30mol ferrous sulfate heptahydrate（Purity is 100 weight %, similarly hereinafter）, 30mol phosphoric acid（Purity is 100 weight %, under
With）, 0.03mol cetyl trimethylammonium bromide（Tianjin great Mao chemical reagent factory, similarly hereinafter）And the mixing of 40kg deionized water
Uniformly and obtain water solution A after dissolving completely.By 90mol monohydrate lithium hydroxide（Purity is 100 weight %, similarly hereinafter）Go with 30kg
Ionized water mixes and obtains aqueous solution B after dissolving completely.At 25 DEG C, described aqueous solution B is slowly added into water solution A
In, and open dispersion machine and cooling water simultaneously, the temperature of this process mixed solution rises to 39 DEG C from 20 DEG C.Feed after finishing again
Dispersion a period of time, now the temperature of mixed solution is increased to 45 DEG C and keeps constant, then will be mixed molten using lithium hydroxide
The pH value of liquid is adjusted to 8.5, obtains alkaline product.20L deionized water is added to the autoclave that 110L gauge pressure is 1MPa
In, and it is warming up to 130 DEG C with the speed of 2 DEG C/min, alkaline product is dropped to the speed of 500mL/min equipped with temperature be
In the autoclave of 130 DEG C of deionized water, in the process, the temperature of solution ripple between 125-135 DEG C in reactor
Dynamic（The heating rate of alkaline product is equivalent to 80-90 DEG C/s）.After alkaline product adds and finishes, isothermal reaction at 130 DEG C
30min, is then down to 30 DEG C of room temperature, and using hydrochloric acid, the pH value of product is adjusted to 6.5, obtain acid product.20L is gone
Ionized water is added in the autoclave that 110L gauge pressure is 1MPa, and is warming up to 130 DEG C with the speed of 2 DEG C/min, by acidity
Product drops in the autoclave of the deionized water being 130 DEG C equipped with temperature with the speed of 500mL/min, in this process
In, in reactor, the temperature of solution fluctuates between 125-135 DEG C（The heating rate of acid product is equivalent to 95-105 DEG C/s）.
After acid product adds and finishes, temperature is risen to 180 DEG C and isothermal reaction 10h at such a temperature, is then down to 30 DEG C of room temperature,
Filter, wash and dry, obtain LiFePO4 L1.Permissible from the XRD spectra of described LiFePO4 L1 and LiFePO4 standard specimen
Find out, the diffraction maximum of LiFePO4 L1 being prepared using the present embodiment is identical with the peak position of the diffraction maximum of standard specimen, and peak shape is narrow
Narrow and symmetrical, do not observe dephasign peak in diffraction pattern it is seen that LiFePO4 and purity have really been obtained very using the method
High.
400g glucose is dissolved in 20kg water, and is added thereto to 4kg above-mentioned LiFePO4 L1, after stirring
It is spray-dried at 80 DEG C, then Spray dried products is placed in 700 DEG C of atmosphere furnace, control nitrogen flow is 50L/
H roasting 8h, obtains composite ferric lithium phosphate material S1.
Wherein, the SEM result of described composite ferric lithium phosphate material S1 is as depicted in figs. 1 and 2.Wherein, scheme
1 multiplication factor is 50000 times, and the multiplication factor of Fig. 2 is 20000 times.Can be seen that described from the SEM photograph of Fig. 1 and Fig. 2
Composite ferric lithium phosphate material S1 is by substantial amounts of little particle（Particle diameter is 100-150nm）The medium-sized particle with sheet（Particle diameter is 400-
600nm）Composition, and contact closely between both particles, there is no obvious agglomeration.
Embodiment 2
This embodiment is used for LiFePO4 that the present invention provides and preparation method thereof is described.
By 9.5mol ferrous acetate（Purity is 100 weight %）, 9.5mol sodium phosphate（Purity is 100 weight %）、0.02mol
Cetyl trimethylammonium bromide（Tianjin great Mao chemical reagent factory）And after 40kg deionized water mixes and dissolves completely
Obtain water solution A.By 30mol lithium chloride（Purity is 100 weight %）After mixing with 30kg deionized water and dissolve completely
To aqueous solution B.At 25 DEG C, described aqueous solution B is slowly added in water solution A, and opens dispersion machine and cooling water simultaneously,
The temperature of this process mixed solution rises to 39 DEG C from 20 DEG C.Charging finishes rear redisperse for a period of time, now mixed solution
Temperature is increased to 45 DEG C and keeps constant, is then adjusted the pH value of mixed solution to 8.0 using lithium hydroxide, obtains alkalescence product
Thing.20L deionized water is added in the autoclave that 110L gauge pressure is 2.5MPa, and is warming up to the speed of 2 DEG C/min
240 DEG C, alkaline product is dropped to the autoclave of the deionized water being 240 DEG C equipped with temperature with the speed of 500mL/min
In, in the process, in reactor, the temperature of solution fluctuates between 235-245 DEG C（The heating rate of alkaline product is equivalent to
190-200℃/s）.After alkaline product adds and finishes, isothermal reaction 30min at 240 DEG C, then it is down to 20 DEG C of room temperature, and
Using hydrochloric acid, the pH value of product is adjusted to 6.5, obtains acid product.20L deionized water is added to 110L gauge pressure is
In the autoclave of 2.5MPa, and it is warming up to 240 DEG C with the speed of 2 DEG C/min, by acid product with the speed of 500mL/min
Drop in the autoclave of the deionized water being 240 DEG C equipped with temperature, in the process, in reactor, the temperature of solution exists
Fluctuate between 235-245 DEG C（The heating rate of acid product is equivalent to 215-225 DEG C/s）.After acid product adds and finishes,
Cool the temperature to 180 DEG C and isothermal reaction 5h at such a temperature, be then down to 20 DEG C of room temperature, filter, wash and dry, obtain phosphorus
Sour iron lithium L2.Can be seen that from the XRD spectra of described LiFePO4 L2 and LiFePO4 standard specimen and be prepared into using the present embodiment
The diffraction maximum of LiFePO4 L2 arriving is identical with the peak position of the diffraction maximum of standard specimen, and peak shape is narrow and symmetrical, does not see in diffraction pattern
Observe dephasign peak it is seen that LiFePO4 has really been obtained using the method and purity is very high.
500g glucose is dissolved in 20kg water, and is added thereto to 5kg above-mentioned LiFePO4 L2, after stirring
It is spray-dried at 100 DEG C, then Spray dried products is placed in 600 DEG C of atmosphere furnace, control nitrogen flow is
50L/h roasting 12h, obtains composite ferric lithium phosphate material S2.
Wherein, can be seen that described composite ferric lithium phosphate material from the SEM photograph of described composite ferric lithium phosphate material S2
S2 is by substantial amounts of little particle（Particle diameter is 50-200nm）The medium-sized particle with sheet（Particle diameter is 300-500nm）Composition, and both
Contact closely between particle, there is no obvious agglomeration.
Embodiment 3
This embodiment is used for LiFePO4 that the present invention provides and preparation method thereof is described.
By 10.5mol frerrous chloride（Purity is 100 weight %）, 10.5mol phosphoric acid（Purity is 100 weight %）、0.02mol
Cetyl trimethylammonium bromide（Tianjin great Mao chemical reagent factory）And after 40kg deionized water mixes and dissolves completely
Obtain water solution A.By 30mol monohydrate lithium hydroxide（Purity is 100 weight %）Mix with 30kg deionized water and dissolved
Aqueous solution B is obtained after complete.At 25 DEG C, described aqueous solution B is slowly added in water solution A, and simultaneously open dispersion machine and
Cooling water, the temperature of this process mixed solution rises to 39 DEG C from 20 DEG C.Charging finishes rear redisperse for a period of time, now mixes
The temperature of solution is increased to 45 DEG C and keeps constant, is then adjusted the pH value of mixed solution to 13 using lithium hydroxide, obtains
Alkaline product.20L deionized water is added in the autoclave that 110L gauge pressure is 0.8MPa, and the speed with 2 DEG C/min
It is warming up to 120 DEG C, alkaline product is dropped to the high pressure of the deionized water being 120 DEG C equipped with temperature with the speed of 500mL/min
In reactor, in the process, in reactor, the temperature of solution fluctuates between 115-125 DEG C（The heating rate of alkaline product
Be equivalent to 70-80 DEG C/s）.After alkaline product adds and finishes, isothermal reaction 30min at 120 DEG C, is then down to room temperature 20
DEG C, and using hydrochloric acid, the pH value of product is adjusted to 4, obtain acid product.20L deionized water is added to 110L gauge pressure is
In the autoclave of 0.8MPa, and it is warming up to 120 DEG C with the speed of 2 DEG C/min, by acid product with the speed of 500mL/min
Drop in the autoclave of the deionized water being 120 DEG C equipped with temperature, in the process, in reactor, the temperature of solution exists
Fluctuate between 115-125 DEG C（The heating rate of acid product is equivalent to 95-105 DEG C/s）.After acid product adds and finishes, will
Temperature rises to 240 DEG C and isothermal reaction 2h at such a temperature, is then down to 20 DEG C of room temperature, filters, washs and dry, obtain phosphoric acid
Iron lithium L3.Can be seen that from the XRD spectra of described LiFePO4 L3 and LiFePO4 standard specimen and prepared using the present embodiment
The diffraction maximum of LiFePO4 L3 identical with the peak position of the diffraction maximum of standard specimen, peak shape is narrow and symmetrical, does not observe in diffraction pattern
To dephasign peak it is seen that LiFePO4 has really been obtained using the method and purity is very high.
500g glucose is dissolved in 20kg water, and is added thereto to 4kg above-mentioned LiFePO4 L3, after stirring
It is spray-dried at 120 DEG C, then Spray dried products is placed in 750 DEG C of atmosphere furnace, control nitrogen flow is
50L/h roasting 3h, obtains composite ferric lithium phosphate material S3.
Wherein, can be seen that described composite ferric lithium phosphate material from the SEM photograph of described composite ferric lithium phosphate material S3
S3 is by substantial amounts of little particle（Particle diameter is 50-200nm）The medium-sized particle with sheet（Particle diameter is 300-500nm）Composition, and both
Contact closely between particle, there is no obvious agglomeration.
Embodiment 4
This embodiment is used for LiFePO4 that the present invention provides and preparation method thereof is described.
Method according to embodiment 1 prepares LiFePO4, and except for the difference that, described cetyl trimethylammonium bromide is with identical
The laurate quaternary ammonium salt of molal quantity substitutes, and obtains LiFePO4 L4 and composite ferric lithium phosphate material S4.Wherein, from described phosphoric acid
The XRD spectra of iron lithium L4 and LiFePO4 standard specimen can be seen that spreading out of the LiFePO4 L4 preparing using the present embodiment
Penetrating peak identical with the peak position of the diffraction maximum of standard specimen, peak shape is narrow and symmetrical, not observing dephasign peak in diffraction pattern it is seen that adopting
The method has really obtained LiFePO4 and purity is very high.Additionally, the SEM photograph of described composite ferric lithium phosphate material S4 is as schemed
Shown in 3 and Fig. 4.Wherein, the multiplication factor of Fig. 3 is 50000 times, and the multiplication factor of Fig. 4 is 20000 times.SEM from Fig. 3 and Fig. 4
Photo can be seen that described composite ferric lithium phosphate material S4 by substantial amounts of little particle（Particle diameter is 50-200nm）With medium-sized of sheet
Grain（Particle diameter is 300-500nm）Composition, and contact closely between both particles, there is no obvious agglomeration.
Embodiment 5
This embodiment is used for LiFePO4 that the present invention provides and preparation method thereof is described.
Method according to embodiment 1 prepares LiFePO4, and except for the difference that, described cetyl trimethylammonium bromide is with identical
The cetyl benzenesulfonic acid sodium of molal quantity substitutes, and obtains LiFePO4 L5 and composite ferric lithium phosphate material S5.Wherein, from described phosphorus
The XRD spectra of sour iron lithium L5 and LiFePO4 standard specimen can be seen that the LiFePO4 L5's preparing using the present embodiment
Diffraction maximum is identical with the peak position of the diffraction maximum of standard specimen, and peak shape is narrow and symmetrical, does not observe dephasign peak it is seen that adopting in diffraction pattern
Really obtained LiFePO4 with the method and purity is very high.Additionally, the SEM photograph from described composite ferric lithium phosphate material S5
In as can be seen that described composite ferric lithium phosphate material S5 by substantial amounts of little particle（Particle diameter is 50-200nm）The medium-sized particle with sheet
（Particle diameter is 300-500nm）Composition, and contact closely between both particles, there is no obvious agglomeration.
Embodiment 6
This embodiment is used for LiFePO4 that the present invention provides and preparation method thereof is described.
Method according to embodiment 1 prepares LiFePO4, except for the difference that, is added without cetyl trimethylammonium bromide, obtains
To LiFePO4 L6 and composite ferric lithium phosphate material S6.Wherein, compose from the XRD of described LiFePO4 L6 and LiFePO4 standard specimen
Scheme as can be seen that the diffraction maximum of LiFePO4 L6 being prepared using the present embodiment is identical with the peak position of the diffraction maximum of standard specimen,
Peak shape is narrow and symmetrical, do not observe dephasign peak in diffraction pattern it is seen that using the method really obtained LiFePO4 and
Purity is very high.Additionally, can be seen that described LiFePO4 composite wood from the SEM photograph of described composite ferric lithium phosphate material S6
Material S6 is by substantial amounts of little particle（Particle diameter is 50-200nm）The medium-sized particle with sheet（Particle diameter is 300-500nm）Composition, and this two
Planting contact between particle closely, does not have obvious agglomeration.
Embodiment 7
This embodiment is used for LiFePO4 that the present invention provides and preparation method thereof is described.
By 30mol ferrous sulfate heptahydrate, 30mol phosphoric acid, 0.03mol cetyl trimethylammonium bromide and 40kg deionization
Water mixes and obtains water solution A after dissolving completely.90mol monohydrate lithium hydroxide and 30kg deionized water are mixed simultaneously
Aqueous solution B is obtained after dissolving completely.At 25 DEG C, described aqueous solution B is slowly added in water solution A, and unlatching point simultaneously
Scattered machine and cooling water, the temperature of this process mixed solution rises to 39 DEG C from 20 DEG C.Charging finishes rear redisperse for a period of time, this
When mixed solution temperature be increased to 45 DEG C and keep constant, then using lithium hydroxide by the pH value of mixed solution adjust to
8.5, obtain alkaline product.By 20L deionized water be added to 110L gauge pressure be 1.5MPa autoclave in, and with 2 DEG C/
The speed of min is warming up to 180 DEG C, alkaline product is dropped to the deionization being 180 DEG C equipped with temperature with the speed of 500mL/min
In the autoclave of water, in the process, in reactor, the temperature of solution fluctuates between 175-185 DEG C（Alkaline product
Heating rate is equivalent to 130-140 DEG C/s）.After alkaline product adds and finishes, at 180 DEG C, isothermal reaction 30min, then drops
To 30 DEG C of room temperature, and using hydrochloric acid, the pH value of product is adjusted to 6.5, obtains acid product.20L deionized water is added to
110L gauge pressure is in the autoclave of 1.5MPa, and is warming up to 180 DEG C with the speed of 2 DEG C/min, by acid product with
The speed of 500mL/min drops in the autoclave of the deionized water being 180 DEG C equipped with temperature, in the process, reaction
In kettle, the temperature of solution fluctuates between 175-185 DEG C（The heating rate of acid product is equivalent to 145-155 DEG C/s）.Treat acidity
After product addition finishes, isothermal reaction 10h at 180 DEG C, is then down to 30 DEG C of room temperature, filters, washs and dry, obtain phosphoric acid
Iron lithium L7.Can be seen that from the XRD spectra of described LiFePO4 L7 and LiFePO4 standard specimen and prepared using the present embodiment
The diffraction maximum of LiFePO4 L7 identical with the peak position of the diffraction maximum of standard specimen, peak shape is narrow and symmetrical, does not observe in diffraction pattern
To dephasign peak it is seen that LiFePO4 has really been obtained using the method and purity is very high.
400g glucose is dissolved in 20kg water, and is added thereto to 4kg above-mentioned LiFePO4 L7, after stirring
It is spray-dried at 80 DEG C, then Spray dried products is placed in 700 DEG C of atmosphere furnace, control nitrogen flow is 50L/
H roasting 8h, obtains composite ferric lithium phosphate material S7.
Wherein, can be seen that described composite ferric lithium phosphate material from the SEM photograph of described composite ferric lithium phosphate material S7
S7 is by substantial amounts of little particle（Particle diameter is 50-200nm）The medium-sized particle with sheet（Particle diameter is 300-500nm）Composition, and both
Contact closely between particle, there is no obvious agglomeration.
Embodiment 8
This embodiment is used for LiFePO4 that the present invention provides and preparation method thereof is described.
By 30mol ferrous sulfate heptahydrate, 30mol phosphoric acid, 0.03mol cetyl trimethylammonium bromide and 40kg deionization
Water mixes and obtains water solution A after dissolving completely.90mol monohydrate lithium hydroxide and 30kg deionized water are mixed simultaneously
Aqueous solution B is obtained after dissolving completely.At 25 DEG C, described aqueous solution B is slowly added in water solution A, and unlatching point simultaneously
Scattered machine and cooling water, the temperature of this process mixed solution rises to 39 DEG C from 20 DEG C.Charging finishes rear redisperse for a period of time, this
When mixed solution temperature be increased to 45 DEG C and keep constant, then using lithium hydroxide by the pH value of mixed solution adjust to
8.5, obtain alkaline product.By 20L deionized water be added to 110L gauge pressure be 0.1MPa autoclave in, and with 2 DEG C/
The speed of min is warming up to 80 DEG C, alkaline product is dropped to the deionized water being 80 DEG C equipped with temperature with the speed of 500mL/min
Autoclave in, in the process, in reactor, the temperature of solution fluctuates between 75-85 DEG C（The intensification of alkaline product
Speed is equivalent to 30-40 DEG C/s）.After alkaline product adds and finishes, isothermal reaction 5h at 80 DEG C, is then down to room temperature 30
DEG C, and using hydrochloric acid, the pH value of product is adjusted to 6.5, obtain acid product.20L deionized water is added to 110L gauge pressure
For in the autoclave of 0.1MPa, and it is warming up to 80 DEG C with the speed of 2 DEG C/min, by acid product with the speed of 500mL/min
Degree drops in the autoclave of the deionized water being 80 DEG C equipped with temperature, in the process, the temperature of solution in reactor
Fluctuate between 75-85 DEG C（The heating rate of acid product is equivalent to 45-55 DEG C/s）.After acid product adds and finishes, will
Temperature rises to 80 DEG C and isothermal reaction 14h at such a temperature, is then down to 30 DEG C of room temperature, filters, washs and dry, obtain phosphoric acid
Iron lithium L8.Can be seen that from the XRD spectra of described LiFePO4 L8 and LiFePO4 standard specimen and prepared using the present embodiment
The diffraction maximum of LiFePO4 L8 identical with the peak position of the diffraction maximum of standard specimen, peak shape is narrow and symmetrical, does not observe in diffraction pattern
To dephasign peak it is seen that LiFePO4 has really been obtained using the method and purity is very high.
400g glucose is dissolved in 20kg water, and is added thereto to 4kg above-mentioned LiFePO4 L8, after stirring
It is spray-dried at 80 DEG C, then Spray dried products is placed in 700 DEG C of atmosphere furnace, control nitrogen flow is 50L/
H roasting 8h, obtains composite ferric lithium phosphate material S8.
Wherein, can be seen that described composite ferric lithium phosphate material from the SEM photograph of described composite ferric lithium phosphate material S8
S8 is by substantial amounts of little particle（Particle diameter is 50-200nm）The medium-sized particle with sheet（Particle diameter is 300-500nm）Composition, and both
Contact closely between particle, there is no obvious agglomeration.
Embodiment 9
This embodiment is used for LiFePO4 that the present invention provides and preparation method thereof is described.
Method according to embodiment 1 prepares LiFePO4, except for the difference that, is adjusted the pH value of mixed solution using lithium hydroxide
Save to 7.5, obtain LiFePO4 L9 and composite ferric lithium phosphate material S9.Wherein, from described LiFePO4 L9 and LiFePO4
The XRD spectra of standard specimen can be seen that the diffraction maximum of the diffraction maximum of LiFePO4 L9 preparing using the present embodiment and standard specimen
Peak position identical, peak shape is narrow and symmetrical, does not observe dephasign peak it is seen that really having obtained phosphorus using the method in diffraction pattern
Sour iron lithium and purity is very high.Additionally, can be seen that described phosphoric acid from the SEM photograph of described composite ferric lithium phosphate material S9
Iron lithium composite material S9 is by substantial amounts of little particle（Particle diameter is 50-200nm）The medium-sized particle with sheet（Particle diameter is 300-500nm）Group
Become, and contact closely between both particles, there is no obvious agglomeration.
Embodiment 10
This embodiment is used for LiFePO4 that the present invention provides and preparation method thereof is described.
Method according to embodiment 1 prepares LiFePO4, except for the difference that, is adjusted to the pH value of product using hydrochloric acid
5.5, obtain LiFePO4 L10 and composite ferric lithium phosphate material S10.Wherein, from described LiFePO4 L10 and LiFePO4 mark
The XRD spectra of sample can be seen that the diffraction maximum of LiFePO4 L10 preparing using the present embodiment and the diffraction maximum of standard specimen
Peak position is identical, and peak shape is narrow and symmetrical, does not observe dephasign peak it is seen that really having obtained phosphoric acid using the method in diffraction pattern
Iron lithium and purity is very high.Additionally, can be seen that described ferric phosphate from the SEM photograph of described composite ferric lithium phosphate material S10
Lithium composite material S10 is by substantial amounts of little particle（Particle diameter is 50-200nm）The medium-sized particle with sheet（Particle diameter is 300-500nm）Group
Become, and contact closely between both particles, there is no obvious agglomeration.
Embodiment 11
This embodiment is used for LiFePO4 that the present invention provides and preparation method thereof is described.
Method according to embodiment 10 prepares LiFePO4, except for the difference that, is adjusted to the pH value of product using hydrochloric acid
3, obtain LiFePO4 L11 and composite ferric lithium phosphate material S11.Wherein, from described LiFePO4 L11 and LiFePO4 standard specimen
XRD spectra can be seen that the diffraction maximum of LiFePO4 L11 being prepared using the present embodiment and standard specimen diffraction maximum peak
Position is identical, and peak shape is narrow and symmetrical, does not observe dephasign peak it is seen that really having obtained ferric phosphate using the method in diffraction pattern
Lithium and purity is very high.Additionally, can be seen that described LiFePO4 from the SEM photograph of described composite ferric lithium phosphate material S11
Composite S11 is by substantial amounts of little particle（Particle diameter is 50-200nm）The medium-sized particle with sheet（Particle diameter is 300-500nm）Composition,
And contact closely between both particles, there is no obvious agglomeration.
Comparative example 1
This comparative example is used for LiFePO4 of reference and preparation method thereof is described.
By 30mol ferrous sulfate heptahydrate, 30mol phosphoric acid, 0.03mol cetyl trimethylammonium bromide and 40kg deionization
Water mixes and obtains aqueous solution DA1.After 90mol monohydrate lithium hydroxide and 30kg deionized water being mixed and dissolve completely
Obtain aqueous solution DB1.At 25 DEG C, described aqueous solution DB1 is slowly added in aqueous solution DA1, simultaneously open dispersion machine and
Cooling water, the temperature of this process mixed solution rises to 39 DEG C from 20 DEG C.Charging finishes rear redisperse for a period of time, now mixes
The temperature of solution is increased to 45 DEG C and keeps constant, obtains presoma DC1.Then presoma DC1 is added to autoclave
In, and temperature is risen to 180 DEG C with the speed of 5 DEG C/s by described presoma, and isothermal reaction 10h under 180 DEG C, 0.8MPa,
Then product is down to 30 DEG C of room temperature, filters, wash and dry, obtain the LiFePO4 DL1 of reference.From described reference
The phosphorus of the reference preparing using this comparative example is can be seen that in the XRD spectra of LiFePO4 DL1 and LiFePO4 standard specimen
The diffraction maximum of sour iron lithium DL1 is identical with the peak position of the diffraction maximum of standard specimen, there is a small amount of dephasign peak in diffraction pattern it can be seen that,
The purity of the LiFePO4 DL1 of reference is relatively low.
400g glucose is dissolved in 20kg water, and is added thereto to the above-mentioned LiFePO 4 of 4kg, after stirring
It is spray-dried at 80 DEG C, then Spray dried products is placed in 700 DEG C of atmosphere furnace, control nitrogen flow is 50L/
H roasting 8h, obtains the composite ferric lithium phosphate material DS1 of reference.
Wherein, the SEM result of the composite ferric lithium phosphate material DS1 of described reference is as shown in Figure 5 and Figure 6.
Wherein, the multiplication factor of Fig. 5 is 20000 times, and the multiplication factor of Fig. 6 is 50000 times.Can from the SEM photograph of Fig. 5 and Fig. 6
Go out, the composite ferric lithium phosphate material DS1 of described reference is by substantial amounts of little particle（Particle diameter is 100-300nm）The medium-sized particle with strip
（Particle diameter is 500-800nm）Composition, and have obvious space between both particles, there is no obvious agglomeration.
Comparative example 2
This comparative example is used for LiFePO4 of reference and preparation method thereof is described.
Method according to comparative example 1 prepares LiFePO4, except for the difference that, is added without cetyl trimethylammonium bromide, obtains
Composite ferric lithium phosphate material DS2 to reference LiFePO4 DL2 and reference.Wherein, from the LiFePO4 DL2 of described reference and
The diffraction of the LiFePO4 DL2 of reference preparing using this comparative example is can be seen that in the XRD spectra of LiFePO4 standard specimen
Peak is identical with the peak position of the diffraction maximum of standard specimen, there is a small amount of dephasign peak in diffraction pattern it can be seen that, the LiFePO4 of reference
The purity of DL2 is relatively low.Additionally, the microscopic appearance of the composite ferric lithium phosphate material DS2 of described reference is as shown in Figure 7 and Figure 8.Its
In, the multiplication factor of Fig. 7 is 50000 times, and the multiplication factor of Fig. 8 is 20000 times.Can be seen that from the SEM photograph of Fig. 7 and Fig. 8
The composite ferric lithium phosphate material DS2 of described reference is by substantial amounts of little particle（Particle diameter is 150-300nm）The medium-sized particle with strip（Grain
Footpath is 500-800nm）Composition, and have obvious space between both particles, there is no obvious agglomeration.
Test case
Test case is used for LiFePO4 and the test of composite ferric lithium phosphate material chemical property are described.
By positive electrode active materials（The composite ferric lithium phosphate material L1-L11 that embodiment 1-11 obtains and comparative example 1-2 obtain
Reference composite ferric lithium phosphate material DL1-DL2）, acetylene black, Kynoar（Celebrate rich plastic material purchased from Dongguan City limited
Company, the trade mark is FR900）By weight for 90:5:5 are dissolved in 1-METHYLPYRROLIDONE and stir, then 110 DEG C ±
Being pressed into thickness after vacuum drying at 5 DEG C is 0.2mm, the disk of a diameter of Φ 12mm as positive pole.Using metal lithium sheet as negative
Pole, barrier film is microporous polypropylene membrane（Celgard2300）, (wherein, EC is the LiPF6/ (EC+DMC) for 1.0mol/L for the electrolyte
Ethylene carbonate, DMC is dimethyl carbonate, and the volume ratio of EC and DMC is 1:1), seal in the glove box full of argon gas, system
Become R2025 button cell.At 30 DEG C of room temperature, R2025 button cell is carried out its charge/discharge capacity of charge and discharge electrical measurement with 0.1C,
Wherein, end of charge voltage is 3.8V, and discharge cut-off voltage is 2.5V.First charge-discharge under 0.1C for the R2025 button cell
Capacity and efficiency for charge-discharge（Efficiency for charge-discharge（%）=discharge capacity ÷ charging capacity × 100%）As shown in table 1.Additionally, as the following formula
Calculate its volume energy density（mWh/cm3）, result is as shown in table 1：
Volume energy density（mWh/cm3）=compacted density（g/cm3）× discharge capacity（mAh/g）.
Table 1
As can be seen from the above results, the particle diameter of the LiFePO4 prepared by method being provided using the present invention is little and electrochemical
Learn excellent performance.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to various can
The combination of energy no longer separately illustrates.
Additionally, can also be combined between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.
Claims (16)
1. a kind of preparation method of LiFePO4, the method is included watersoluble divalent source of iron, water-soluble phosphorus source and water solubility
Lithium source contacts and reacts, and described water solubility phosphorus source is phosphoric acid and/or water-soluble phosphate it is characterised in that the side of described reaction
Formula includes adjusting the pH value of product of contact to alkalescence, and alkaline product is rapidly heated to 80-240 DEG C carries out the first reaction,
Then the product of the described first reaction is down to 20-50 DEG C and is adjusted its pH value to acidity, then acid product is rapidly heated
Carry out the second reaction to 80-240 DEG C；Described being rapidly heated refers to that heating rate is not less than 10 DEG C/s.
2. preparation method according to claim 1, wherein, by described alkaline product be rapidly heated with by described acid product
The heating rate being rapidly heated is identical or different, and is each independently 30-250 DEG C/s.
3. preparation method according to claim 1 and 2, wherein, the pH value of described alkaline product is 7.5-14, described acidity
The pH value of product is 4-6.5.
4. preparation method according to claim 1 and 2, wherein, described alkaline product is rapidly heated to 80-240 DEG C
Method is to drop to described alkaline product in the water that temperature is 80-240 DEG C；Described acid product is rapidly heated to 80-240
DEG C method be that described acid product is dropped to temperature is in 80-240 DEG C of water.
5. preparation method according to claim 1 and 2, wherein, the condition of described first reaction includes：Reaction temperature is
80-240 DEG C, reaction pressure is 0-5MPa, and the reaction time is 0.5-5 hour.
6. preparation method according to claim 1 and 2, wherein, the condition of described second reaction includes：Reaction temperature is
80-240 DEG C, reaction pressure is 0-5MPa, and the reaction time is 2-14 hour.
7. preparation method according to claim 1 and 2, wherein, the consumption of described watersoluble divalent source of iron, described water solubility
The consumption of the consumption of phosphorus source and described water solubility lithium source makes Fe in the product of contact obtaining2+、PO4 3-With Li+Mol ratio be
（0.95-1.05）:（0.95-1.05）:3.
8. preparation method according to claim 7, wherein, described watersoluble divalent source of iron is selected from frerrous chloride, protobromide
One or more of iron, ferrous fluosilicate, ferrous nitrate, ferrous perchlorate, ferrous sulfate and ferrous acetate；Described water solubility
Phosphate is selected from one or more of lithium dihydrogen phosphate, sodium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and potassium phosphate；Described
Water-soluble lithium source is selected from lithium hydroxide, lithium acetate, lithium benzoate, lithium bromate, lithium bromide, lithium chlorate, lithium chloride, lithium fluoride, fluorine
One or more of lithium metasilicate, lithium formate, lithium iodide, lithium nitrate, lithium perchlorate, lithium tartrate and lithium carbonate.
9. preparation method according to claim 1, wherein, the method is also included surfactant and watersoluble divalent iron
Source, water-soluble phosphorus source and water-soluble lithium source are contacted together and are reacted；The consumption of described surfactant is water-soluble with described
The mol ratio of the consumption of property lithium source is（0.0001-0.01）:1.
10. preparation method according to claim 9, wherein, described surfactant is selected from cetyl trimethyl bromination
Ammonium, laurate quaternary ammonium salt, cetyl benzenesulfonic acid sodium, citric acid, polyethylene glycol, sodium hexadecyl sulfate, Gemini quaternary ammonium
One or more of salt and DGE carboxylate.
11. preparation methods according to claim 1,2,9 or 10, wherein, the method also includes producing the described second reaction
Thing is mixed with organic carbon source and is spray-dried, then the Spray dried products obtaining are carried out roasting.
12. preparation methods according to claim 11, wherein, with the dry weight of described second product of 100 weight portions
Meter, the consumption of described organic carbon source is 2-20 weight portion；Described organic carbon source is selected from glucose, sucrose, lactose, maltose, phenol
One or more of urea formaldehyde and epoxy resin.
13. preparation methods according to claim 11, wherein, the temperature of described spray drying is 60-150 DEG C.
14. preparation methods according to claim 11, wherein, the condition of described roasting includes：Sintering temperature is 600-750
DEG C, roasting time is 3-12 hour.
The LiFePO4 that 15. preparation methods described in any one in claim 1-14 prepare.
LiFePO4 described in 16. claims 15 is as the application of positive electrode active materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310739960.5A CN104752716B (en) | 2013-12-27 | 2013-12-27 | Lithium iron phosphate and its preparation method and use |
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| CN106684379B (en) * | 2015-11-11 | 2019-05-10 | 中国科学院金属研究所 | Synthesize the method with the ultrathin nanometer sheet LiFePO4 of superelevation high rate charge-discharge performance |
| CN108470888B (en) * | 2018-03-05 | 2020-09-11 | 南京理工大学 | Method for preparing assembled diamond-shaped lithium iron phosphate/silver/graphene oxide compound by growth at pH regulation stage |
| CN113896181B (en) * | 2021-10-09 | 2023-02-10 | 四川裕宁新能源材料有限公司 | Method for producing low-cost nano battery grade iron phosphate |
| CN114361448B (en) * | 2021-12-31 | 2023-07-14 | 欣旺达电动汽车电池有限公司 | Lithium iron phosphate, preparation method thereof and lithium ion battery |
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| CN102070132A (en) * | 2009-12-18 | 2011-05-25 | 清华大学 | Lithium iron phosphate and ferrous phosphate, and preparation methods thereof |
| CN102381693A (en) * | 2010-09-06 | 2012-03-21 | 李文宝 | Preparation method of lithium iron phosphate |
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