CN107240696A - The preparation method and carbon-coated LiFePO 4 for lithium ion batteries and lithium ion battery of carbon-coated LiFePO 4 for lithium ion batteries - Google Patents
The preparation method and carbon-coated LiFePO 4 for lithium ion batteries and lithium ion battery of carbon-coated LiFePO 4 for lithium ion batteries Download PDFInfo
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Abstract
The invention provides the preparation method of carbon-coated LiFePO 4 for lithium ion batteries and carbon-coated LiFePO 4 for lithium ion batteries and lithium ion battery, it is related to technical field of lithium ion.The preparation method is first to mix part carbon source with ferric phosphate, after grinding, drying, carry out pre-sintered, presintering material, lithium source are mixed with part carbon source again, after grinding, drying, sintering obtains carbon-coated LiFePO 4 for lithium ion batteries again, pass through the cladding of carbon source twice and two-step sintering process, realize the double-coating of carbon-coating in the surface of the carbon-coated LiFePO 4 for lithium ion batteries prepared, and carbon coating layer is uniform, firm, complete conductive network can be formed, the electrical conductivity of carbon-coated LiFePO 4 for lithium ion batteries is significantly improved, improves its chemical property;Meanwhile, the preparation method can effectively control carbon-coated LiFePO 4 for lithium ion batteries to be in micron or Nano grade, and epigranular is controllable, and carbon-coated LiFePO 4 for lithium ion batteries is spherical, be conducive to improving the tap density of carbon-coated LiFePO 4 for lithium ion batteries.Present invention also offers the carbon-coated LiFePO 4 for lithium ion batteries obtained using above-mentioned preparation method.
Description
Technical field
The present invention relates to technical field of lithium ion, preparation method in particular to carbon-coated LiFePO 4 for lithium ion batteries and
Carbon-coated LiFePO 4 for lithium ion batteries and lithium ion battery.
Background technology
Lithium ion battery mainly includes positive pole, three parts of electrolyte and negative pole.Wherein, anode material for lithium-ion batteries is
Determine the key factor of battery performance, security performance, energy density and Costco Wholesale.At present, lithium ion battery
Positive electrode has a lot, such as cobalt system positive electrode, nickel system positive electrode, manganese cathode material, lithium iron phosphate positive material etc..
Wherein, LiFePO4 (LiFePO4) positive electrode theoretical capacity be 170mAh/g, reversible charging and discharging capacity compared with
Height, while have again, raw material sources are extensive, pollute the advantages such as low, security is good, have extended cycle life, and are ideal at present move
Power shape and energy storage shape anode material for lithium-ion batteries.But, due to the limitation of self structure, the ionic conductance of LiFePO4 and
Electron conductivity is relatively low, is only suitable under low current density carrying out discharge and recharge, and specific capacity is reduced during high power charging-discharging, this limit
The application of the material is made.
At present, carried out substantial amounts of study on the modification to LiFePO4 to improve the electric conductivity of LiFePO4 both at home and abroad, it is main
To include preparing nanoscale LiFePO4, prepare porous LiFePO4, the mode such as metal ion mixing, still, the above method is prepared
LiFePO4 also has very big room for promotion in electronic conductivity and ionic conductivity.
In view of this, it is special to propose the present invention to solve above-mentioned technical problem.
The content of the invention
First purpose of the present invention is to provide a kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries, and the preparation method is first
Part carbon source is mixed with ferric phosphate, after grinding, drying, pre-sintering is carried out, then presintering material, lithium source and part carbon source are mixed
Close, grinding, dry after, again sintering obtain carbon-coated LiFePO 4 for lithium ion batteries, pass through carbon source twice cladding and two-step sintering process, prepare
The double-coating of carbon-coating is realized on the surface of obtained carbon-coated LiFePO 4 for lithium ion batteries, and carbon coating layer is uniform, firm, can be formed complete
Conductive network, significantly improves the electrical conductivity of carbon-coated LiFePO 4 for lithium ion batteries, improves its chemical property;Meanwhile, the preparation method is also
Carbon-coated LiFePO 4 for lithium ion batteries can be effectively controlled to be in micron or Nano grade, epigranular is controllable, and carbon-coated LiFePO 4 for lithium ion batteries is
It is spherical, be conducive to improving the tap density of carbon-coated LiFePO 4 for lithium ion batteries.
Second object of the present invention is to provide a kind of carbon-coated LiFePO 4 for lithium ion batteries, the carbon on the carbon-coated LiFePO 4 for lithium ion batteries surface
Clad is bilayer, and carbon coating layer is uniform, firm, can form complete conductive network, can significantly improve carbon coating phosphoric acid
The electrical conductivity of iron lithium;Meanwhile, carbon-coated LiFePO 4 for lithium ion batteries is spherical, is conducive to the raising of carbon-coated LiFePO 4 for lithium ion batteries tap density.
Third object of the present invention is to provide a kind of lithium ion battery.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme:
The invention provides a kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries, comprise the following steps:
(a) wet grinding is carried out after mixing ferric phosphate, part carbon source, an abrasive is obtained;
(b) abrasive obtained by step (a) is dried;
(c) a dried abrasive is subjected to pre-sintering under protective atmosphere, obtains presintering material;
(d) wet grinding is carried out after the carbon source of presintering material, lithium source and remainder is mixed, secondary abrasive is obtained;
(e) secondary abrasive is dried;
(f) dried secondary abrasive is sintered again under protective atmosphere, that is, obtains carbon-coated LiFePO 4 for lithium ion batteries.
Further, the carbon coating layer of the carbon-coated LiFePO 4 for lithium ion batteries is bilayer.
Further, in step (a), the quality of carbon source is the 0.5-5% of phosphoric acid weight of iron.
Further, in step (b), the drying is spray drying or oven drying;
It is preferred that, spray drying inlet temperature is 200-350 DEG C, and outlet temperature is 60-120 DEG C.
Further, in step (c), pre-sintered temperature is 250-550 DEG C, and the pre-sintered time is 2-10h;
It is preferred that, the protective atmosphere is one kind or at least two in nitrogen, argon gas, helium, neon, Krypton or xenon
The combination planted.
Further, in step (d), the quality of carbon source is the 0.5-5% of presintering material quality;
Stoichiometric proportion according to the LiFePO4 of required preparation adds lithium source.
Further, in step (f), the temperature sintered again is 650-900 DEG C, and the time sintered again is 2-10h;
It is preferred that, the protective atmosphere is one kind or at least two in nitrogen, argon gas, helium, neon, Krypton or xenon
The combination planted.
Further, in step (a) and step (d), the carbon source is selected from glucose, sucrose, fructose, graphite, conductive charcoal
One kind or at least two combination in black, citric acid or starch.
Present invention also offers a kind of carbon-coated LiFePO 4 for lithium ion batteries, using the preparation method system of above-mentioned carbon-coated LiFePO 4 for lithium ion batteries
Standby to form, the carbon coating layer of the carbon-coated LiFePO 4 for lithium ion batteries is bilayer.
Present invention also offers a kind of lithium ion battery, lithium ion battery is used as using above-mentioned carbon-coated LiFePO 4 for lithium ion batteries
Positive electrode.
Compared with prior art, the present invention is provided the preparation method of carbon-coated LiFePO 4 for lithium ion batteries, carbon-coated LiFePO 4 for lithium ion batteries with
And lithium ion battery has the advantage that:
(1) the invention provides a kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries, the preparation method is first by part carbon source
Mixed with ferric phosphate, grinding, dry after, carry out pre-sintered, then presintering material, lithium source mix with part carbon source, it is grinding, dry
Afterwards, sintering obtains carbon-coated LiFePO 4 for lithium ion batteries again, passes through the cladding of carbon source twice and two-step sintering process, the carbon coating prepared
The double-coating of carbon-coating is realized on the surface of LiFePO4, and carbon coating layer is uniform, firm, can form complete conductive network, shows
The electrical conductivity for improving carbon-coated LiFePO 4 for lithium ion batteries is write, improves its chemical property;Meanwhile, the preparation method can also effectively control carbon
Coated LiFePO 4 for lithium ion batteries is in micron or Nano grade, and epigranular is controllable, and carbon-coated LiFePO 4 for lithium ion batteries is spherical, is conducive to
Improve the tap density of carbon-coated LiFePO 4 for lithium ion batteries.
(2) the preparation method process is simple, it is easy to operates, is suitable for industrialized production.
(3) present invention also offers a kind of carbon-coated LiFePO 4 for lithium ion batteries, the carbon coating layer on the carbon-coated LiFePO 4 for lithium ion batteries surface is
Bilayer, and carbon coating layer is uniform, firm, can form complete conductive network, can significantly improve the electricity of carbon-coated LiFePO 4 for lithium ion batteries
Conductance;Meanwhile, carbon-coated LiFePO 4 for lithium ion batteries is spherical, is conducive to the raising of carbon-coated LiFePO 4 for lithium ion batteries tap density.
(4) the invention provides a kind of lithium ion battery, the lithium ion battery is used as using above-mentioned carbon-coated LiFePO 4 for lithium ion batteries
Positive electrode, in view of above-mentioned carbon-coated LiFePO 4 for lithium ion batteries has the advantage that so that lithium ion battery have more extensive purposes.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The accompanying drawing used required in embodiment or description of the prior art is briefly described, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is X-ray diffraction (XRD) figure of carbon-coated LiFePO 4 for lithium ion batteries prepared by the embodiment of the present invention 8;
Fig. 2 is ESEM (SEM) figure of carbon-coated LiFePO 4 for lithium ion batteries prepared by the embodiment of the present invention 8;
Fig. 3 is ESEM (SEM) figure of carbon-coated LiFePO 4 for lithium ion batteries prepared by the embodiment of the present invention 10;
Fig. 4 is Fig. 3 partial enlarged drawing.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, be
The conventional products that can be obtained by commercially available purchase.
According to an aspect of the invention, there is provided a kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries, comprises the following steps:
(a) wet grinding is carried out after ferric phosphate is mixed with part carbon source, an abrasive is obtained;
(b) abrasive obtained by step (a) is dried;
(c) a dried abrasive is subjected to pre-sintering under protective atmosphere, obtains presintering material;
(d) wet grinding is carried out after mixing presintering material, lithium source and remainder carbon source, secondary abrasive is obtained;
(e) secondary abrasive is dried;
(f) dried secondary abrasive is sintered again under protective atmosphere, that is, obtains carbon-coated LiFePO 4 for lithium ion batteries.
It is first to mix part carbon source with ferric phosphate the invention provides a kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries,
Grinding, dry after, carry out pre-sintered, then presintering material, lithium source mix with part carbon source, grinding, it is dry after, sinter again
To carbon-coated LiFePO 4 for lithium ion batteries, pass through the cladding of carbon source twice and two-step sintering process, the table of the carbon-coated LiFePO 4 for lithium ion batteries prepared
The double-coating of carbon-coating is realized in face, and carbon coating layer is uniform, firm, can form complete conductive network, significantly improve carbon bag
Cover the electrical conductivity of LiFePO4;Meanwhile, it is simple using the preparation method process, it is easy to operate, it can also effectively control carbon coating phosphorus
Sour iron lithium is in micron or Nano grade, and epigranular is controllable, is suitable for industrialized production.
It should be noted that in the present invention in the generating process of LiFePO4, being added twice before and after carbon source point, carbon source exists
Gas is produced in carbonisation, has certain pore-creating to act on, material specific surface area can be increased.Meanwhile, generated in-situ carbon can be with
Suppress particle to grow up, alleviate particle agglomeration phenomenon, particle is uniformly dispersed, and lithium iron phosphate particles Surface coatings it is complete,
Uniformly, firm carbon coating layer, the tap density and specific energy of material, and the carbon bag can be not only improved to a certain extent
Coating can also form complete conductive network, can significantly improve the chemical property of material, especially electronic conductivity.
Ferric phosphate, also known as high ferric phosphate, ferric orthophosphate, molecular formula is FePO4, it is a kind of white, canescence monoclinic crystal
Powder.Lithium source, a kind of in lithium hydroxide, lithium carbonate, lithium oxalate or lithium lactate or at least two combination, further
Preferably lithium hydroxide and/or lithium carbonate.
Because the LiFePO4 chemical formula finally prepared is LiFePO4, therefore the amount ratio of ferric phosphate and the material of lithium source is about
1:1.
Specifically, first, carrying out wet grinding after ferric phosphate and the mixing of part carbon source, the solvent of wet grinding is preferably
Ionized water, ethanol or acetone, solvent can ensure ferric phosphate, carbon source being sufficiently mixed in process of lapping, and significantly improve
Grinding efficiency.The equipment of batch mixing grinding can be three-dimensional material mixer, planetary ball mill, VC batch mixers, dry method ball mill or fusion
One kind in machine.
In the preferred embodiment of the present invention, in step (a), the quality of carbon source is the 0.5- of phosphoric acid weight of iron
5%.
The quality of carbon source be phosphoric acid weight of iron typical but non-limiting fraction be 0.5%, 1%, 1.5%, 2%,
2.5%th, 3%, 3.5%, 4%, 4.5% or 5%.
In the preferred embodiment of the present invention, in step (a), the time of grinding is 0.5-10h.
The time of typical but non-limiting grinding be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h,
5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h or 10h.
After ferric phosphate, carbon source wet grinding, an abrasive is obtained, an abrasive is slurry form.To once it grind
Abrasive material needs to be dried.The drying mode of selection is a variety of, concretely oven drying, infra-red drying, microwave drying or spray
One kind in mist drying.
In the preferred embodiment of the present invention, in step (b), above-mentioned drying is spray drying.
It is preferred that, spray drying inlet temperature is 200-350 DEG C, and outlet temperature is 60-120 DEG C.
The characteristics of spray drying tool heat transfer is fast, moisture evaporation is rapid, drying time is short.Spray drying is preferred to be done in spraying
Carried out in machine, drying machine with centrifugal spray or Pressuresprayingdrier.
Be spray-dried typical but non-limiting inlet temperature for 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250
DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C or 350 DEG C.
Be spray-dried typical but non-limiting outlet temperature for 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90
DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C or 120 DEG C.
A dried abrasive is carried out pre-sintered.Pre-sintering is carried out to an abrasive, under pre-sintering temperature,
Carbon source is carbonized completion substantially, and carbon particle has been formed.Due to carbon source carbonisation and relatively low reaction temperature so that carbon particle
It is evenly distributed between iron phosphate grains.
In the preferred embodiment of the present invention, pre-sintered temperature is 250-550 DEG C, and the pre-sintered time is 2-
10h;
It is preferred that, protective atmosphere is one kind or at least two in nitrogen, argon gas, helium, neon, Krypton or xenon
Combination, more preferably nitrogen.
Pre-sintered typical but non-limiting temperature is 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C, 300 DEG C, 310
℃、320℃、330℃、340℃、350℃、360℃、370℃、380℃、390℃、 400℃、410℃、420℃、430℃、
440 DEG C, 450 DEG C, 460 DEG C, 470 DEG C, 480 DEG C, 490 DEG C, 500 DEG C, 510 DEG C, 520 DEG C, 530 DEG C, 540 DEG C or 550 DEG C.
The pre-sintered typical but non-limiting time is 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h.
Wet grinding is carried out after the carbon source of presintering material, lithium source and remainder is mixed, secondary abrasive is obtained.At this
In a kind of preferred embodiment of invention, in step (d), lithium is added according to the stoichiometric proportion of the LiFePO4 of required preparation
Source;
The quality of carbon source is the 0.5-5% of presintering material quality.
The quality of carbon source be presintering material quality typical but non-limiting fraction be 0.5%, 1.0%, 1.5%,
2.0%th, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% or 5.0%.
In the preferred embodiment of the present invention, in step (e), secondary abrasive is dried.
Drying in step (e) can be one kind in oven drying, infra-red drying, microwave drying or spray drying, preferably
For spray drying.
It is further preferred that spray drying inlet temperature is 200-350 DEG C, outlet temperature is 60-120 DEG C.
Dried secondary abrasive is sintered again.Again in sintering process, the carbon particle after charing can be close
Be coated on lithium iron phosphate particles surface.
In the preferred embodiment of the present invention, the temperature sintered again is 650-900 DEG C, the time sintered again
For 2-10h;
It is preferred that, again sinter when protective atmosphere be nitrogen, argon gas, helium, neon, Krypton or xenon in one kind or
At least two combination.
Again sinter when typical but non-limiting temperature be 650 DEG C, 660 DEG C, 680 DEG C, 700 DEG C, 720 DEG C, 740 DEG C,
750 DEG C, 760 DEG C, 780 DEG C, 800 DEG C, 820 DEG C, 840 DEG C, 850 DEG C, 860 DEG C, 880 DEG C or 900 DEG C.
The typical but non-limiting time is 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h when sintering again.
In the preferred embodiment of the present invention, in step (a) and step (d), carbon source be selected from glucose, sucrose,
One kind or at least two combination in fructose, graphite, conductive black, citric acid or starch.
According to the second aspect of the invention, a kind of carbon-coated LiFePO 4 for lithium ion batteries is additionally provided, using above-mentioned carbon coating phosphorus
The preparation method of sour iron lithium is prepared from, and the carbon coating layer of the carbon-coated LiFePO 4 for lithium ion batteries is bilayer.
The carbon coating layer on the carbon-coated LiFePO 4 for lithium ion batteries surface is bilayer, and carbon coating layer is uniform, firm, can be formed complete
Conductive network, can significantly improve the electrical conductivity of carbon-coated LiFePO 4 for lithium ion batteries;Meanwhile, carbon-coated LiFePO 4 for lithium ion batteries is spherical, favorably
In the raising of carbon-coated LiFePO 4 for lithium ion batteries tap density.
According to the third aspect of the present invention, a kind of lithium ion battery is additionally provided, using above-mentioned carbon coating ferric phosphate
Lithium is anode material for lithium-ion batteries.In view of above-mentioned carbon-coated LiFePO 4 for lithium ion batteries has the advantage that so that lithium ion battery has more
For extensive purposes.
With reference to specific embodiment and comparative example, the invention will be further described.
Embodiment 1
A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries, comprises the following steps:
(a) wet grinding is carried out after mixing ferric phosphate and part carbon source, an abrasive is obtained, wherein, wet grinding
Time be 2h, abrasive solvents are deionized water, and carbon source is glucose, and carbon source quality is the 4.5% of phosphoric acid weight of iron;
(b) abrasive obtained by step (a) is subjected to oven drying, dry temperature is 110 DEG C, and the time is 12h;
(c) a dried abrasive is subjected to pre-sintering under protective atmosphere helium, pre-sintering temperature is 250
DEG C, the pre-sintered time is 10h, obtains presintering material;
(d) carry out wet grinding after mixing presintering material, lithium source with the carbon source of remainder, obtain secondary abrasive its
In, lithium source is lithium hydroxide, and the time of wet grinding is 2h, and abrasive solvents are deionized water, and carbon source is glucose, carbon source quality
For the 4% of presintering material quality;
(e) oven drying is dried in secondary abrasive, the temperature of oven drying is 110 DEG C, and the time is 12h;
(f) dried secondary abrasive is sintered again under protective atmosphere helium, the temperature sintered again is
750 DEG C, the time sintered again is 8h, that is, obtains carbon-coated LiFePO 4 for lithium ion batteries.
Embodiment 2
The preparation method for the carbon-coated LiFePO 4 for lithium ion batteries that the present embodiment is provided, except the carbon source in step (a) and (d)
Using electrically conductive graphite, remaining is same as Example 1, and specific steps refer to embodiment 1.
Embodiment 3
A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries, comprises the following steps:
(a) wet grinding is carried out after mixing ferric phosphate and part carbon source, an abrasive is obtained, wherein, wet grinding
Time be 5h, abrasive solvents are ethanol, and carbon source is sucrose, and carbon source quality is the 3% of phosphoric acid weight of iron;
(b) abrasive obtained by step (a) is spray-dried, the inlet temperature of spray drying is 250 DEG C, is gone out
Mouth temperature is 60 DEG C;
(c) a dried abrasive is subjected to pre-sintering under protective atmosphere argon gas, pre-sintering temperature is 300
DEG C, the pre-sintered time is 8h, obtains presintering material;
(d) carry out wet grinding after mixing presintering material, lithium source with the carbon source of remainder, obtain secondary abrasive its
In, lithium source is lithium hydroxide, and the time of wet grinding is 5h, and abrasive solvents are ethanol, and carbon source is sucrose, and carbon source quality is pre-burning
The 3% of ramming material quality;
(e) secondary abrasive is subjected to oven drying, dry temperature is 110 DEG C, and the time is 12h;
(f) dried secondary abrasive is sintered again under protective atmosphere argon gas, the temperature sintered again is
650 DEG C, the time sintered again is 7h, that is, obtains carbon-coated LiFePO 4 for lithium ion batteries.
Embodiment 4
The preparation method for the carbon-coated LiFePO 4 for lithium ion batteries that the present embodiment is provided, except by the temperature sintered again in step (f)
Degree is brought up to outside 900 DEG C, and remaining is same as Example 3, and specific steps refer to embodiment 3.
Embodiment 5
The preparation method for the carbon-coated LiFePO 4 for lithium ion batteries that the present embodiment is provided, in addition to the carbon source in step (d) is graphene,
Remaining is same as Example 3, and specific steps refer to embodiment 3.
Embodiment 6
A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries, comprises the following steps:
(a) wet grinding is carried out after mixing ferric phosphate and part carbon source, an abrasive is obtained, wherein, wet grinding
Time be 10h, abrasive solvents are deionized water, and carbon source is citric acid, and carbon source quality is the 4% of phosphoric acid weight of iron;
(b) abrasive obtained by step (a) is spray-dried, the inlet temperature of spray drying is 350 DEG C, is gone out
Mouth temperature is 100 DEG C;
(c) a dried abrasive is subjected to pre-sintering under protective atmosphere neon, pre-sintering temperature is 400
DEG C, the pre-sintered time is 6h, obtains presintering material;
(d) carry out wet grinding after mixing presintering material, lithium source with the carbon source of remainder, obtain secondary abrasive its
In, lithium source is lithium carbonate, and the time of wet grinding is 3h, and abrasive solvents are ethanol, and carbon source is citric acid, and carbon source quality is pre-burning
The 2% of ramming material quality;
(e) secondary abrasive is spray-dried, the inlet temperature of spray drying is 350 DEG C, and outlet temperature is 100
℃;
(f) dried secondary abrasive is sintered again under protective atmosphere neon, the temperature sintered again is
800 DEG C, the time sintered again is 6h, that is, obtains carbon-coated LiFePO 4 for lithium ion batteries.
Embodiment 7
The preparation method for the carbon-coated LiFePO 4 for lithium ion batteries that the present embodiment is provided, except the pre-sintered time lengthening in step (c)
To outside 10h, remaining is same as Example 6, and specific steps refer to embodiment 6.
Embodiment 8
A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries, comprises the following steps:
(a) wet grinding is carried out after mixing ferric phosphate and part carbon source, an abrasive is obtained, wherein, wet grinding
Time be 6h, abrasive solvents are deionized water, and carbon source is graphene, and carbon source quality is the 2% of phosphoric acid weight of iron;
(b) abrasive obtained by step (a) is spray-dried, the inlet temperature of spray drying is 300 DEG C, is gone out
Mouth temperature is 80 DEG C;
(c) a dried abrasive is subjected to pre-sintering under protective atmosphere nitrogen, pre-sintering temperature is 550
DEG C, the pre-sintered time is 2h, obtains presintering material;
(d) carry out wet grinding after mixing presintering material, lithium source with the carbon source of remainder, obtain secondary abrasive its
In, lithium source is lithium hydroxide, and the time of wet grinding is 6h, and abrasive solvents are deionized water, and carbon source is graphene, carbon source quality
For the 3% of presintering material quality;
(e) secondary abrasive is spray-dried, the inlet temperature of spray drying is 300 DEG C, and outlet temperature is 80 DEG C;
(f) dried secondary abrasive is sintered again under protective atmosphere nitrogen, the temperature sintered again is
850 DEG C, the time sintered again is 3h, that is, obtains carbon-coated LiFePO 4 for lithium ion batteries.
Embodiment 9
The preparation method for the carbon-coated LiFePO 4 for lithium ion batteries that the present embodiment is provided, except using oven drying in step (e), is dried
Temperature is 110 DEG C, and the time is 12h, and remaining is same as Example 8, and specific steps refer to embodiment 8.
Embodiment 10
The preparation method for the carbon-coated LiFePO 4 for lithium ion batteries that the present embodiment is provided, except the carbon source quality in step (d) is phosphoric acid
Outside the 5% of weight of iron, remaining is same as Example 8, and specific steps refer to embodiment 8.
Embodiment 11
A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries, comprises the following steps:
(a) wet grinding is carried out after mixing ferric phosphate and part carbon source, an abrasive is obtained, wherein, wet grinding
Time be 0.5h, abrasive solvents are ethanol, and carbon source is starch, and carbon source quality is the 1% of phosphoric acid weight of iron;
(b) abrasive obtained by step (a) is spray-dried, the inlet temperature of spray drying is 200 DEG C, is gone out
Mouth temperature is 100 DEG C;
(c) a dried abrasive is subjected to pre-sintering under protective atmosphere nitrogen, pre-sintering temperature is 450
DEG C, the pre-sintered time is 5h, obtains presintering material;
(d) carry out wet grinding after mixing presintering material, lithium source with the carbon source of remainder, obtain secondary abrasive its
In, lithium source is lithium carbonate, and the time of wet grinding is 10h, and abrasive solvents are ethanol, and carbon source is starch, and carbon source quality is pre-burning
The 0.5% of ramming material quality;
(e) secondary abrasive is spray-dried, the inlet temperature of spray drying is 200 DEG C, and outlet temperature is 100
℃;
(f) dried secondary abrasive is sintered again under protective atmosphere nitrogen, the temperature sintered again is
700 DEG C, the time sintered again is 4h, that is, obtains carbon-coated LiFePO 4 for lithium ion batteries.
Embodiment 12
The preparation method for the carbon-coated LiFePO 4 for lithium ion batteries that the present embodiment is provided, except carbon source quality is pre-sintering in step (d)
Outside expect quality 5%, remaining is identical with embodiment 11, and specific steps refer to embodiment 11.
Embodiment 13
The preparation method for the carbon-coated LiFePO 4 for lithium ion batteries that the present embodiment is provided, except carbon source quality is pre-sintering in step (d)
Outside expect quality 10%, remaining is identical with embodiment 11, and specific steps refer to embodiment 1.
Embodiment 14
The preparation method for a kind of carbon-coated LiFePO 4 for lithium ion batteries that the present embodiment is provided, except will again be sintered in step (f)
Temperature is reduced to 600 DEG C, and remaining is same as Example 1, and specific steps refer to embodiment 1.
Comparative example 1
A kind of preparation method for carbon-coated LiFePO 4 for lithium ion batteries that this comparative example is provided, comprises the following steps:
(a) wet grinding is carried out after mixing ferric phosphate and part carbon source, an abrasive is obtained, wherein, wet grinding
Time be 10h, abrasive solvents are deionized water, and carbon source is citric acid, and carbon source quality is the 2% of phosphoric acid weight of iron;
(b) abrasive obtained by step (a) is spray-dried, the inlet temperature of spray drying is 350 DEG C, is gone out
Mouth temperature is 100 DEG C;
(c) wet grinding is carried out after a dried abrasive is mixed with lithium source, carbon source, secondary abrasive is obtained,
Wherein, lithium source is lithium carbonate, and the time of wet grinding is 3h, and abrasive solvents are ethanol, and carbon source is citric acid, and carbon source quality is one
The 2% of secondary abrasive quality;
(d) secondary abrasive is spray-dried, the inlet temperature of spray drying is 350 DEG C, and outlet temperature is 100
℃;
(e) dried secondary abrasive is sintered again under protective atmosphere neon, the temperature sintered again is
800 DEG C, the time sintered again is 6h, that is, obtains carbon-coated LiFePO 4 for lithium ion batteries.
Comparative example 2
A kind of preparation method for carbon-coated LiFePO 4 for lithium ion batteries that this comparative example is provided, comprises the following steps:
(a) wet grinding is carried out after mixing ferric phosphate, carbon source and lithium source, abrasive is obtained, wherein, lithium source is carbonic acid
Lithium, the time of wet grinding is 3h, and abrasive solvents are ethanol, and carbon source is citric acid, and carbon source quality is the 4% of phosphoric acid weight of iron;
(b) abrasive is spray-dried, the inlet temperature of spray drying is 350 DEG C, and outlet temperature is 100 DEG C;
(c) dried abrasive is calcined under protective atmosphere neon, the temperature of sintering is 800 DEG C, sintering
Time is 6h, that is, obtains carbon-coated LiFePO 4 for lithium ion batteries.
For checking embodiment and the effect of comparative example, ad hoc following experimental example.
Experimental example 1
The carbon-coated LiFePO 4 for lithium ion batteries prepared to each embodiment carries out XRD and TEM tests.Wherein, only with the He of embodiment 8
Illustrated exemplified by embodiment 10.Fig. 1 is the XRD of carbon-coated LiFePO 4 for lithium ion batteries prepared by embodiment 8.Find, implement after contrast
The XRD of example 8 and iron lithium phosphate standard diagram (PDF NO.40-1499) are very identical, and main peak strength ratio is more prominent, does not have substantially
There is miscellaneous peak.Test result shows that the carbon-coated LiFePO 4 for lithium ion batteries lattice prepared is regular, and crystallinity is preferable.
Fig. 2 and Fig. 3 are respectively the SEM figures of carbon-coated LiFePO 4 for lithium ion batteries prepared by embodiment 8 and embodiment 10.Can from figure
With, it is evident that carbon coating iron lithium phosphate preferably maintains spherical pattern, and there are many tiny spherical carbon particles to be formed
Carbon-coating is coated on the surface of iron lithium phosphate.Fig. 4 is Fig. 3 partial enlarged drawing, figure 4, it is seen that being coated on iron lithium phosphate
The carbon-coating on surface is more loose, and centre is full of stomata.Stomata is formed such that coated carbon surface has big specific surface area,
It is easy to fully infiltrate with electrolyte, is conducive to the insertion of lithium ion to move out.
Because carbon coating iron lithium phosphate is generally the spherical particle of rule, therefore rare reunion and particle are built bridge between particles
Phenomenon, is conducive to the raising of tap density.And spherical particle has excellent mobility and dispersiveness, its particle surface ratio
It is easier to complete, uniform, the firm carbon-coating of cladding.
Experimental example 2
Meanwhile, embodiment 1-14 and comparative example 1-2 carbon-coated LiFePO 4 for lithium ion batteries is carried out particle diameter test, tap density and
Specific discharge capacity under different multiplying is determined, and concrete outcome is shown in Table 1.
Each embodiment of table 1 and comparative example particle diameter, tap density and specific discharge capacity
From table 1 it follows that the charge-discharge parameter for the carbon coating iron lithium phosphate that embodiment 1-14 is provided is substantially better than pair
The carbon coating iron lithium phosphate that ratio 1-2 is provided.
Specifically, embodiment 2 is the control experiment of embodiment 1, embodiment 5 is the control experiment of embodiment 3.Above-mentioned difference
Part is that the raw material selection of carbon source is different.It can be seen that, different carbon source has certain difference for the performance of carbon-coated LiFePO 4 for lithium ion batteries.
When carbon source selection is glucose, electrically conductive graphite, sucrose or graphene, it can be formed uniformly on lithium iron phosphate particles surface
Carbon coating layer.
Embodiment 4 is the control experiment of embodiment 3, and both differences are temperature when (f) step is sintered again not
Together.Embodiment 7 is the control experiment of embodiment 6, and both differences are that the pre-sintered time is different.Embodiment 14 is embodiment
11 control experiment, temperature when both differences then are to sinter again is different.It can be seen that, sintering temperature and sintering time pair
Particle diameter, tap density in carbon-coated LiFePO 4 for lithium ion batteries particle have a significant effect, and suitable sintering temperature and sintering time causes carbon
Coated LiFePO 4 for lithium ion batteries granular grows are abundant.But sintering temperature is too high or sintering time is long, crystal grain reunion is may result in,
Bulky grain is generated, chemical property is influenceed.
Embodiment 8 is the control experiment of embodiment 9.Compared to, using spray drying, embodiment 9 is then in the step (e) of embodiment 8
Use oven drying.In the preparation process of carbon-coated LiFePO 4 for lithium ion batteries, for the drying side of an abrasive in step (b)
The step (e) of drying mode in formula or to(for) secondary abrasive can directly affect the particle diameter of final carbon-coated LiFePO 4 for lithium ion batteries.By
The characteristics of spray drying tool heat transfer is fast, moisture evaporation is rapid, drying time is short, therefore uses and be spray-dried dried particle
Footpath is small compared with using the grain diameter of oven drying, and distribution of particles is more uniform.
Embodiment 12 is the control experiment of embodiment 11, and embodiment 14 is the control experiment of embodiment 1.Two groups of control experiments
It is to investigate carbon source in step (d) to account for the difference of the i.e. carbon coating amount of presintering material mass fraction for final carbon-coated LiFePO 4 for lithium ion batteries
The influence of performance.It can be seen from the data in Table 1 that being continuously increased with carbon coating amount, particle size is less and less.Thus may be used
Know, carbon coating amount needs to control in suitable scope.
In the preparation method for the carbon-coated LiFePO 4 for lithium ion batteries that comparative example 1 is provided, after raw material once adds carbon source mill-drying,
The step for without low temperature presintering knot.In the preparation method for the carbon-coated LiFePO 4 for lithium ion batteries that comparative example 2 is provided, all raw materials are
It is disposable to add, and without low temperature presintering knot, directly using the preparation method of high temperature sintering.Knowable to contrast, low temperature presintering knot
The specific discharge capacity of material can be effectively lifted with secondary carbon coating process, improves the chemical property of material.
In summary, the carbon coating phosphorus obtained using the preparation method of carbon-coated LiFePO 4 for lithium ion batteries provided in an embodiment of the present invention
The overall performance of sour iron lithium is superior to the carbon coating phosphorus that the preparation method of the carbon-coated LiFePO 4 for lithium ion batteries provided using comparative example is obtained
Sour iron lithium.
Finally it should be noted that:Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations;To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that:Its according to
The technical scheme described in foregoing embodiments can so be modified, or which part or all technical characteristic are entered
Row equivalent substitution;And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries, it is characterised in that comprise the following steps:
(a) wet grinding is carried out after ferric phosphate is mixed with part carbon source, an abrasive is obtained;
(b) abrasive obtained by step (a) is dried;
(c) a dried abrasive is subjected to pre-sintering under protective atmosphere, obtains presintering material;
(d) wet grinding is carried out after the carbon source of presintering material, lithium source and remainder is mixed, secondary abrasive is obtained;
(e) secondary abrasive is dried;
(f) dried secondary abrasive is sintered again under protective atmosphere, obtains carbon-coated LiFePO 4 for lithium ion batteries.
2. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries according to claim 1, it is characterised in that the carbon coating ferric phosphate
The carbon coating layer of lithium is bilayer.
3. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries according to claim 1, it is characterised in that in step (a), carbon source
Quality is the 0.5-5% of phosphoric acid weight of iron.
4. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries according to claim 1, it is characterised in that in step (b), described dry
Dry is spray drying or oven drying;
It is preferred that, spray drying inlet temperature is 200-350 DEG C, and outlet temperature is 60-120 DEG C.
5. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries according to claim 1, it is characterised in that in step (c), pre-sintered
Temperature be 250-550 DEG C, pre-sintered time is 2-10h;
It is preferred that, the protective atmosphere used when pre-sintered for one kind in nitrogen, argon gas, helium, neon, Krypton or xenon or
At least two combination.
6. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries according to claim 1, it is characterised in that in step (d), carbon source
Quality is the 0.5-5% of presintering material quality;
Stoichiometric proportion according to the LiFePO4 of required preparation adds lithium source.
7. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries according to claim 1, it is characterised in that in step (f), burns again
The temperature of knot is 650-900 DEG C, and the time sintered again is 2-10h;
It is preferred that, the protective atmosphere is one kind or at least two in nitrogen, argon gas, helium, neon, Krypton or xenon
Combination.
8. the preparation method of the carbon-coated LiFePO 4 for lithium ion batteries according to claim 1-7, it is characterised in that step (a) and step
(d) in, the one kind or at least two of the carbon source in glucose, sucrose, fructose, graphite, conductive black, citric acid or starch
The combination planted.
9. a kind of carbon-coated LiFePO 4 for lithium ion batteries, it is characterised in that using the carbon coating ferric phosphate described in claim 1-8 any one
The preparation method of lithium is prepared from, and the carbon coating layer of the carbon-coated LiFePO 4 for lithium ion batteries is bilayer.
10. a kind of lithium ion battery, it is characterised in that lithium ion is used as using the carbon-coated LiFePO 4 for lithium ion batteries described in claim 9
The positive electrode of battery.
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101209824A (en) * | 2006-12-31 | 2008-07-02 | 比亚迪股份有限公司 | Preparation method for lithium ion secondary battery positive pole active substance lithium iron phosphate |
CN101494288A (en) * | 2008-01-27 | 2009-07-29 | 比亚迪股份有限公司 | Preparation method for lithium ion secondary battery anode material ferric lithium phosphate |
CN102544448A (en) * | 2010-12-30 | 2012-07-04 | 北京当升材料科技股份有限公司 | Method for preparing lithium battery positive electrode material |
CN102569794A (en) * | 2011-03-23 | 2012-07-11 | 江苏菲思特新能源有限公司 | Carbon-coating method for lithium iron phosphate anode material |
CN102623701A (en) * | 2012-01-13 | 2012-08-01 | 厦门钨业股份有限公司 | Preparation method for low-temperature nanometer lithium iron phosphate cathode material |
CN102881902A (en) * | 2012-10-22 | 2013-01-16 | 山东海特电子新材料有限公司 | Method for industrially producing lithium-iron-phosphate positive pole material |
CN103956489A (en) * | 2014-04-22 | 2014-07-30 | 上海大学 | Method for preparing lithium iron phosphate electrode material by using twice carbon adding technology based on liquid phase mixing material |
CN105428648A (en) * | 2015-11-27 | 2016-03-23 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for preparing battery cathode material lithium iron phosphate |
CN106532013A (en) * | 2016-12-26 | 2017-03-22 | 贝特瑞(天津)纳米材料制造有限公司 | Lithium iron phosphate/carbon composite material for power battery, and preparation method and application of lithium iron phosphate/carbon composite material |
CN106848222A (en) * | 2017-01-18 | 2017-06-13 | 深圳市沃特玛电池有限公司 | A kind of preparation method of LiFePO4/bis- carbon-coating clad composite material |
-
2017
- 2017-07-12 CN CN201710567636.8A patent/CN107240696A/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101209824A (en) * | 2006-12-31 | 2008-07-02 | 比亚迪股份有限公司 | Preparation method for lithium ion secondary battery positive pole active substance lithium iron phosphate |
CN101494288A (en) * | 2008-01-27 | 2009-07-29 | 比亚迪股份有限公司 | Preparation method for lithium ion secondary battery anode material ferric lithium phosphate |
CN102544448A (en) * | 2010-12-30 | 2012-07-04 | 北京当升材料科技股份有限公司 | Method for preparing lithium battery positive electrode material |
CN102569794A (en) * | 2011-03-23 | 2012-07-11 | 江苏菲思特新能源有限公司 | Carbon-coating method for lithium iron phosphate anode material |
CN102623701A (en) * | 2012-01-13 | 2012-08-01 | 厦门钨业股份有限公司 | Preparation method for low-temperature nanometer lithium iron phosphate cathode material |
CN102881902A (en) * | 2012-10-22 | 2013-01-16 | 山东海特电子新材料有限公司 | Method for industrially producing lithium-iron-phosphate positive pole material |
CN103956489A (en) * | 2014-04-22 | 2014-07-30 | 上海大学 | Method for preparing lithium iron phosphate electrode material by using twice carbon adding technology based on liquid phase mixing material |
CN105428648A (en) * | 2015-11-27 | 2016-03-23 | 中信大锰矿业有限责任公司大新锰矿分公司 | Method for preparing battery cathode material lithium iron phosphate |
CN106532013A (en) * | 2016-12-26 | 2017-03-22 | 贝特瑞(天津)纳米材料制造有限公司 | Lithium iron phosphate/carbon composite material for power battery, and preparation method and application of lithium iron phosphate/carbon composite material |
CN106848222A (en) * | 2017-01-18 | 2017-06-13 | 深圳市沃特玛电池有限公司 | A kind of preparation method of LiFePO4/bis- carbon-coating clad composite material |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107845791A (en) * | 2017-10-17 | 2018-03-27 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of Double-layer asphalt carbon-coated LiFePO 4 for lithium ion batteries positive electrode |
CN107845791B (en) * | 2017-10-17 | 2020-11-06 | 合肥国轩高科动力能源有限公司 | Preparation method of double-layer asphalt carbon-coated lithium iron phosphate cathode material |
CN109301216A (en) * | 2018-09-30 | 2019-02-01 | 西北有色金属研究院 | A kind of preparation method of the iron phosphate lithium electrode of carbon boron composite balls cladding |
CN109301216B (en) * | 2018-09-30 | 2021-10-12 | 西北有色金属研究院 | Preparation method of lithium iron phosphate electrode coated with carbon boron composite spheres |
CN111146439B (en) * | 2018-11-06 | 2021-10-15 | 北京泰丰先行新能源科技有限公司 | Preparation method of lithium iron phosphate cathode material |
CN111146439A (en) * | 2018-11-06 | 2020-05-12 | 北京泰丰先行新能源科技有限公司 | Preparation method of lithium iron phosphate cathode material |
CN110380025B (en) * | 2019-06-27 | 2021-10-08 | 湖南雅城新材料有限公司 | Carbon-coated lithium iron phosphate process, prepared carbon-coated lithium iron phosphate and application thereof |
CN110380025A (en) * | 2019-06-27 | 2019-10-25 | 湖南雅城新材料有限公司 | A kind of LiFePO4 covers carbon technique, carbon-covering lithium iron phosphate obtained and its application |
CN113104829A (en) * | 2021-03-19 | 2021-07-13 | 合肥国轩电池材料有限公司 | Lithium iron phosphate material and preparation method and application thereof |
CN113104829B (en) * | 2021-03-19 | 2024-02-09 | 合肥国轩电池材料有限公司 | Lithium iron phosphate material and preparation method and application thereof |
CN114050259A (en) * | 2021-12-08 | 2022-02-15 | 程冲 | Preparation of single crystal high compaction lithium iron phosphate by primary reduction shaping secondary liquid phase coating method |
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CN114348986B (en) * | 2021-12-31 | 2023-01-17 | 江苏贝特瑞纳米科技有限公司 | Lithium iron phosphate production equipment and preparation method thereof |
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