CN102427134A - Mixed conductor composite material LiFePO4-MXy and preparation method thereof - Google Patents
Mixed conductor composite material LiFePO4-MXy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a mixed conductor composite material LiFePO4-MXy. The mixed conductor composite material LiFePO4-MXy is prepared by synthesizing LiFePO4 from the oxides or sulfides of transition metals by a solid state method, and performing high-energy ball-milling and annealing on the transition metals to obtain the mixed conductor composite material LiFePO4-MXy. In the mixed conductor composite material (MCM) LiFePO4-MXy, MXy is not only a conductor of lithium ions but also a conductor of electrons, LiFePO4 particles are uniformly dispersed in the MXy, and the surface of the mixed conductor composite material in a lithium ion battery comprises a carbon material which is added in size mixing and electrolyte which is impregnated in the carbon material. The LiFePO4-MXy has the advantages of high electron conductivity, high ion conductivity, high high-rate charge and discharge capacity, high cycle performance, relatively higher tap density, simple and practical production process, cleanness, no pollution, low cost and the like, and is suitable for large-scale production.
Description
Technical field
The invention belongs to the preparation field of anode material for lithium-ion batteries, relate in particular to a kind of LiFePO
4-MX
yMixed conductor composite materials and preparation method thereof.
Background technology
Energy problem is the 21st century common problem human being face, and electric energy is a kind of energy form of most convenient.Wherein lithium ion battery since light weight, energy density high, have extended cycle life, outstanding advantages such as self-discharge rate is little, memory-less effect and environmental protection, become the focus of whole world research and development.Simultaneously; Fields such as electron trade, IT industry, communication industry are for the demand surge of power supply; Lithium ion battery is environmentally friendly with it, high-energy-density, live forever storage life-span and the ability to work under various environmental conditions, becomes the first-selection of portable electronics and electronic instrument power supply power.
The main building block of lithium ion battery has positive pole, negative pole, barrier film, electrolyte, safety valve and battery case etc.Wherein positive electrode is to the having the greatest impact of battery performance, and its cost accounts for about 40% of entire cell cost.Therefore, research cheap, high performance positive electrode is the emphasis of lithium-ion energy storage battery industry development always.Common anode material for lithium-ion batteries mainly contains cobalt acid lithium, lithium nickelate, the LiMn2O4 of spinel structure and the LiFePO4 of olivine structural of layer structure at present.Cobalt acid lithium (LiCoO
2) the preparation cost height, environmental pollution is big, and the anti-over-charging ability is relatively poor; Lithium nickelate (LiNiO
2) specific capacity is bigger, but be prone to generate the product of non-stoichiometric, structural stability and poor heat stability when preparing; Stratiform LiMnO
2Belong to the thermodynamics metastable state, there is the Jahn-Teller effect in structural instability and cycle performance is relatively poor.The shortcoming of these several kinds of positive electrodes has all restricted the further application of self.
The LiFePO4 of olivine structural from 1997 by Goodenough report, its have can embed reversiblely and deviate to manage ion after LiFePO4 be considered to one of the most promising reason ion battery electrode material.This material has lot of advantages: do not contain precious metal, low in raw material cost, resource are greatly abundant; Nontoxic, environmentally friendly; Operating voltage moderate (3.4V) platform identity is good, under little electric current, has smooth charging/discharging voltage curve, is a kind of desirable reason ion battery positive electrode; Theoretical capacity big (170mAh/g), Stability Analysis of Structures, security performance splendid (O and P make material be difficult to analyse oxygen and decompose with the strong covalent bond strong bonded); High-temperature behavior and good cycle; Volume-diminished during charging, the bulk effect when cooperating with carbon negative pole material is good; Good with most of electrolyte system compatibilities, storge quality is good.But there are two significant disadvantages in LiFePO4: the one, and conductivity is low, and wherein electronic conductivity has only 10
-10The S/cm order of magnitude, the lithium ion diffusion rate is merely 10
-14Cm
2/ s the order of magnitude causes high-rate discharge ability poor, and actual specific capacity is low, and especially than heavy-current discharge the time, electrode polarization is serious, causes discharging and recharging irreversible degree and strengthens, and the electrochemistry capacitance loss is serious; The 2nd, bulk density is low, causes volume and capacity ratio low, and this brings certain difficulty for the application of LiFePO4.
In order to overcome LiFePO
4These defectives, many effective method of modifying are in the news.A kind of method is to improve preparation technology, and preparation has the LiFePO4 of certain pattern or nanoscale, shortens the evolving path of lithium ion, improves the chemical property of LiFePO4.Like [J] Chen et al Accouts of ChemicalResearch 42 (6) 713-723 2009, [J] C.Delacourt et al Electrochemical and Solid-StateLetters 9 (7) A352-A355 2006.
Another kind method is coated with conductive carbon, metal particle or high conductivity compound.A. utilize the high conductive capability of carbon, reduce the contact resistance between the LiFePO4 powder, reach the purpose that reduces polarization, increases cycle life.For example, Chinese patent CN101154722A, Chinese patent CN101162776A, Chinese patent CN101172599A, Chinese patent CN101212049A etc. are the methods that adopts carbon to coat.Utilize carbon to coat and can improve the material electronics conductivity rapidly, but because conductive carbon density is little, and suppress the material grains growth, so the tap density of the material that obtains is very little, often be lower than 1.0g/cm
3, the material volume energy density reduces, and excessive conductive carbon is unfavorable for the battery making.B. adopt conducting metal (like Ag, Cu or Ni etc.) microparticle surfaces to coat, improve electronic conductivity between the LiFePO 4 material particle, for example, Chinese patent CN1649189A, Chinese patent CN101339988A and Chinese patent CN1649188A.This method has also been improved the electric property of LiFePO4 to a certain extent, but has some problems equally, as is difficult to guarantee that side reactions such as oxidation do not appear in metal particle in the follow-up course of processing; The complex process of reduction conducting metal, material cost increases; Prices such as argent are expensive, and utilizing it to carry out surface modification also can increase material cost.C. highly electron conductive or be beneficial to the compound coated LiFePO 4 for lithium ion batteries of lithium ion transmission can improve LiFePO4 based composites electronic conductivity or ionic conductivity, helps improving electrochemical performances of lithium iron phosphate.Propose among the Chinese patent CN101580238A to coat each composite ferric lithium phosphate material of high conductivity oxide system on the LiFePO 4 material surface; Oxide is aluminium oxide, iron oxide or magnesia; Can improve the LiFePO 4 material ionic conductivity; And reason ion transfer passage can also be provided, the LiFePO 4 material high-rate charge-discharge capability is had bigger improvement.Chinese patent CN101388459A adds weight ratio 90: 10-95 in the synthetic LiFePO4 of high temperature solid-state method: at least a in the additional positive electrodes such as 5 cobalts acid lithium, LiMn2O4, lithium nickelate or nickle cobalt lithium manganate, and add the cosolvent LiPO of LiFePO4 and additional positive electrode total weight 0.5-2.0wt.%
3F or NaPO
3F obtains iron phosphate compound anode material of lithium through the secondary granulation processing; Among the Chinese patent CN1631841A that LiFePO4 is compound with the Li-Ti-O nanofiber with high-lithium ion conducting power, prepare LiFePO with high-lithium ion conducting power
4/ Li-Ti-O nano-fiber composite material.But the compound that adds in the foregoing invention only has highly electron conductive or is beneficial to the compound ability that lithium ion transmits, and only can improve electronic conductivity or lithium ion diffusion rate ability, thereby can not increase substantially the chemical property of LiFePO4.Therefore, through effective modification technology, synthesize the LiFePO that has high specific discharge capacity, good high rate performance, excellent stable circulation performance, high tap density concurrently and be fit to extensive industrialization
4Positive electrode has very important significance to the development of lithium ion battery and relevant industries.
Summary of the invention
The purpose of this invention is to provide a kind of LiFePO
4-MX
yMixed conductor composite materials and preparation method.
Technical scheme of the present invention is a kind of LiFePO
4-MX
yThe mixed conductor composite materials is characterized in that: said LiFePO
4-MX
yThe mixed conductor compound comprises: LiFePO4 and account for transition metal oxide or the sulfide of LiFePO4 0.01%-50.00wt.%.
A kind of LiFePO
4-MX
yThe preparation method of mixed conductor composite materials:
(1) be Li: Fe: P=0.9-1.5 with mol ratio: 1: 1 Li source compound, phosphate compounds, Fe source compound and the reducing agent that accounts for the 0.01-50.00wt.% of Li source compound, phosphate compounds and Fe source compound gross mass join in the ball grinder; Add the organic dispersing agent that accounts for Li source compound, phosphate compounds, Fe source compound and reducing agent gross mass 1.00-30.00wt.%, be stirred into the LiFePO4 pasty material;
(2) the LiFePO4 pasty material is carried out drying after, ball milling obtains LiFePO4 precursor powder again;
(3) with LiFePO4 precursor powder, with 250-450 ℃ of pre-burning 4-8 hour, the cooling back was ground and is obtained the pre-burning product in protective atmosphere;
(4) with the granulation of pre-burning product compressing tablet, in protective atmosphere in 450-950 ℃ of sintering 5-25 hour, grind after the cooling lithium iron phosphate positive material;
(5) with the oxide or the sulfide high-energy ball milling 1-8h of lithium iron phosphate positive material and transition metal, obtain mixture; Wherein the consumption of the oxide of transition metal or sulfide is the 0.01%-50.00wt.% of LiFePO4.
(6) with mixture, 100-400 ℃ of annealing 1-12h obtains LiFePO under protective atmosphere
4-MX
yMixed conductor compound (MCM).
Said Li source compound is one or more in lithium carbonate, lithium nitrate, lithium acetate or the lithium hydroxide.
Said Fe source compound is a ferrous sulfate, one or more in ferrous nitrate, ferrous oxalate, ferric acetate, ferric phosphate, iron oxide, ferric nitrate or the iron chloride.
Said phosphate radical source compound is one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate or the phosphoric acid.
Said reducing agent is one or more in sucrose, glucose, caramel, citric acid, oxalic acid, tartaric acid or the polyethylene glycol etc.
Said organic dispersing agent is one or more the mixture in ethanol, methyl alcohol, n-butanol, propyl alcohol, acetone or the deionized water etc.
Said transition metal oxide is Nd
2O
5, Co
3O
4, V
2O
5, MoO
3, V
2O
3, WO
2, MnO
2, CeO
2, TiO
2, among NiO, CoO or CuO etc. one or more.
Said transient metal sulfide is NbS
2, TiS
2, WS
2, MoS
2, FeS
2, NiS
2, ZnS
2, TeS
2Or CoS
2In one or more.
Said protective atmosphere is nitrogen, argon gas, nitrogen and hydrogen mixed gas, and wherein nitrogen accounts for 80-99V%, and hydrogen accounts for 1-20V%; Or argon gas and hydrogen mixed gas, wherein argon gas accounts for 80-99V%, and hydrogen accounts for 1-20V%.
The present invention has following technique effect; This mixed conductor compound can be isolated nano-scale particle and electrolyte; Prevent that under nano particle catalysis the electrolyte decomposition side reaction takes place or lithium ion anode material dissolves in electrolyte, because the transition metal oxide or the sulfide that mix are electronic conductor and lithium ion conductor, can increase substantially material ionic conductivity and electronic conductivity simultaneously; Reduce electrode, the internal resistance of cell; Significantly improve the discharge and the stable circulation performance of electrode material, the mixed conductor compound that meanwhile forms can increase the material tap density, therefore mixes and crosses metal oxide or sulfide and LiFePO
4Forming mixed conductor compound (MCM), is to LiFePO
4Carry out an effective way of modification; Preparation method of the present invention is simple, and cleanliness without any pollution is with low cost, is fit to industrial-scale production.
Description of drawings
Fig. 1 is LiFePO
4-MX
yMixed conductor compound (MCM) conduction Li
+And e
-1Sketch map.Wherein 1 is LiFePO
4, 2 is the oxide or the sulfide (MX of transition metal
y), 3 is LiFePO
4-MX
yMixed conductor compound (MCM), 4 is conductive carbon, 5 is electrolyte.
Fig. 2 is LiFePO in the instance 1
4-V
2O
5The XRD figure of mixed conductor compound (MCM).
Fig. 3 is LiFePO in the instance 2
4-MnO
2The SEM figure of mixed conductor compound (MCM).
Fig. 4 is LiFePO in the instance 1
4-V
2O
5The 1C of mixed conductor compound (MCM) and 2C cycle performance figure.
Embodiment
Be illustrated in figure 1 as LiFePO
4-MX
yMixed conductor compound (MCM) conduction Li
+And e
-1Sketch map.1 is LiFePO in the diagram
4, 2 is the oxide or the sulfide (MX of transition metal
y), 3 is LiFePO
4-MX
yMixed conductor compound (MCM), 4 is conductive carbon, 5 is electrolyte.This mixed conductor compound (MCM) is by the oxide or the sulfide (MX of transition metal
y) and LiFePO4 (LiFePO
4) form.The oxide of transition metal or sulfide (MX
y) be the conductor of lithium ion also be the conductor of electronics, LiFePO
4Uniform particles ground disperses wherein.The mixed conductor composite surface is conductive carbon and the electrolyte that immerses therebetween.e
-And Li
+Reach the mixed conductor compound of high electronics and ionic conductivity respectively through conductive carbon and electrolyte.This mixed conductor compound can be isolated nano-scale particle and electrolyte, prevents that under nano particle catalysis the electrolyte decomposition side reaction takes place or lithium ion anode material dissolves in electrolyte.And in the mixed conductor compound; Because the oxide or the sulfide of the transition metal that adds are electronic conductor and lithium ion conductor; Lithium ion anode material uniform particles ground disperses wherein; Can improve electronic conductivity and can accelerate the lithium ion diffusion rate again, thereby can significantly improve the chemical property of lithium ion anode material.The mixed conductor compound that forms simultaneously can also improve the material tap density.
Embodiment 1:
Take by weighing FeSO respectively
47H
2O 8.34g, NH
4H
2PO
43.45g and LiOHH
2O 1.26g places ball grinder, does dispersant with ethanol, ball milling 3h, and the slurry behind the ball milling places Ar/H at 60 ℃ of dry down back ball milling powdereds
2(Ar accounts for 95V%, H
2Account for 5V%) 350 ℃ of following pre-burning 8h in the mixed gas protected high temperature process furnances, be cooled to room temperature.The pre-burning product is ground, the compressing tablet granulation is placed on Ar/H then again
2(Ar accounts for 95V%, H
2Account for 5V%) in the high temperature process furnances of mixed atmosphere, at 700 ℃ of roasting 15h.After being chilled to room temperature, grind, obtain LiFePO
4Positive electrode.Then with 96wt.%LiFePO
4With 4wt.% conduction V
2O
5Powder high-energy ball milling 2h, the 1h that under 200 ℃ of temperature, anneals in the tube furnace of Ar atmosphere obtains LiFePO
4-V
2O
5Mixed conductor compound (MCM).
LiFePO
4-V
2O
5The electronics conductance of MCM is from 10 of pure phase
-7S/cm brings up to 10
-2The S/cm order of magnitude, the lithium ion diffusion rate is by 10 of pure phase
-14Cm/s
2Rise to 10
-12Cm/s
2The order of magnitude, tap density are 1.3g/cm
3The XRD of product sees shown in Figure 1, can know by Fig. 2, all characteristic diffraction peak positions all with the LiFePO of standard
4(PDF:81-1173) match, belong to rhombic system, the Pnma space group is explained the LiFePO4 that utilizes this method to synthesize olivine-type, V
2O
5Adding do not change its crystal formation, do not have other impurity peaks in the spectrogram, and diffraction maximum is all very sharp-pointed, and the LiFePO that obtains is described
4-V
2O
5Mixed conductor complex crystallization degree is high.
The chemical property of gained sample is measured as follows: take by weighing 0.32g LiFePO
4-V
2O
5MCM adds 0.02g acetylene black, 0.02g graphite and 0.04g Kynoar; Mix, add N-N-methyl 2-pyrrolidone N-furnishing slurry, coating is on the collector aluminium foil equably; After 80 ℃ of dryings, on volume press, flatten, process the about 200 microns anode thin film of thickness.On anode thin film, go out the disk of diameter 1cm size, it more than 110 ℃ of vacuumize 12h, behind the vacuum tank natural cooling, is weighed, as backup electrode.Electrolyte adopts 1mol/L LiPF
6Ethylene vinegar EC: carbonic acid diformazan vinegar DMC (1: 1) mixed liquor; Polypropylene microporous film is a barrier film; Metal reason sheet is as negative pole.Packaged battery in the glove box of argon gas atmosphere, ageing 6 hours.Discharging and recharging the cut-ff voltage scope is 2.0-4.3V, under 1C and 2C multiplying power, discharges and recharges.
Embodiment 2:
Take by weighing FeSO respectively
47H
2O 5.56g, NH
4H
2PO
42.30g and LiOHH
2O 0.84g places ball grinder, does dispersant with ethanol, ball milling 2h, and the slurry behind the ball milling places Ar/H at 60 ℃ of dry down back ball milling powdereds
2(Ar accounts for 95V%, H
2Account for 5V%) 350 ℃ of following pre-burning 8h in the mixed gas protected high temperature process furnances, be cooled to room temperature.The pre-burning product is ground, the compressing tablet granulation is placed on Ar/H then again
2(Ar accounts for 95V%, H
2Account for 5V%) in the high temperature process furnances of mixed atmosphere, at 700 ℃ of roasting 15h.After being chilled to room temperature, grind, obtain LiFePO
4Positive electrode.Then with 90wt.%LiFePO
4And 10wt.%MnO
2High-energy ball milling 2h, the 1h that under 200 ℃ of temperature, anneals in the tube furnace of Ar atmosphere obtains LiFePO
4-MnO
2Mixed conductor compound (MCM).
Fig. 3 is LiFePO
4-MnO
2The SEM figure of mixed conductor compound (MCM).Can know that by figure particle surface obviously has littler particulate to adhere to, because the dimensional effect of fine particle behind the ball milling, the reunion between the particulate obviously increases, and it is big that particle diameter becomes relatively, is owing to formed the result of hybrid conductive compound (MCM).The conductance of compound front and back is from 10
-7S/cm brings up to 10
-2The S/cm order of magnitude, the lithium ion diffusion rate is by 10 of pure phase
-14Cm/s
2Rise to 10
-12Cm/s
2The order of magnitude, tap density are 1.2g/cm
3The electrochemical property test method of gained sample such as instance 1, LiFePO
4-MnO
2MCM discharges and recharges under 1C and 2C multiplying power, and first discharge specific capacity is respectively 155.4 and 143.4mAh/g, and the capability retention that circulates after 100 times is for still having 97.0% and 96.1%.
Embodiment 3:
Take by weighing FeSO respectively
47H
2O 11.12g, NH
4H
2PO
44.60g and LiOHH
2O 1.68g places ball grinder, does dispersant with ethanol, ball milling 2h, and the slurry behind the ball milling places Ar/H at 60 ℃ of dry down back ball milling powdereds
2(Ar accounts for 95V%, H
2Account for 5V%) 350 ℃ of following pre-burning 8h in the mixed gas protected high temperature process furnances, be cooled to room temperature.The pre-burning product is ground, the compressing tablet granulation is placed on Ar/H then again
2(Ar accounts for 95V%, H
2Account for 5V%) in the high temperature process furnances of mixed atmosphere, at 700 ℃ of roasting 15h.After being chilled to room temperature, grind, obtain LiFePO
4Positive electrode.Then with 98wt.%LiFePO
4With 2wt.%NiO high-energy ball milling 3h, the 1h that under 300 ℃ of temperature, anneals in the tube furnace of Ar atmosphere obtains LiFePO
4-NiO mixed conductor compound (MCM).
The conductance of compound front and back is from 10
-7S/cm brings up to 10
-2The S/cm order of magnitude, the lithium ion diffusion rate is by 10 of pure phase
-14Cm/s
2Rise to 10
-12Cm/s
2The order of magnitude, tap density are 1.3g/cm
3The electrochemical property test method of gained sample such as instance 1, LiFePO
4-NiO MCM discharges and recharges under 1C and 2C multiplying power, and first discharge specific capacity is respectively 148.5 and 139.4mAh/g, and the capability retention that circulates after 100 times is for still having 95.4% and 93.2%.
Embodiment 4:
Take by weighing FeSO respectively
47H
2O 8.34g, NH
4H
2PO
43.45g and LiOHH
2O 1.26g places ball grinder, does dispersant with ethanol, ball milling 3h, and the slurry behind the ball milling places Ar/H at 60 ℃ of dry down back ball milling powdereds
2(Ar accounts for 95V%, H
2Account for 5V%) 350 ℃ of following pre-burning 8h in the mixed gas protected high temperature process furnances, be cooled to room temperature.The pre-burning product is ground, the compressing tablet granulation is placed on Ar/H then again
2(Ar accounts for 95V%, H
2Account for 5V%) in the high temperature process furnances of mixed atmosphere, at 700 ℃ of roasting 15h.After being chilled to room temperature, grind, obtain LiFePO
4Positive electrode.Then with 95wt.%LiFePO
4And 5wt.%MoO
3High-energy ball milling 2h, the 1h that under 300 ℃ of temperature, anneals in the tube furnace of Ar atmosphere obtains LiFePO
4-MoO
3Mixed conductor compound (MCM).
The conductance of compound front and back is from 10
-7S/cm brings up to 10
-2The S/cm order of magnitude, the lithium ion diffusion rate is by 10 of pure phase
-14Cm/s
2Rise to 10
-12Cm/s
2The order of magnitude, tap density are 1.4g/cm
3The electrochemical property test method of gained sample such as instance 1, LiFePO
4-MoO
3MCM discharges and recharges under 1C and 2C multiplying power, and first discharge specific capacity is respectively 152.5 and 143.4mAh/g, and the capability retention that circulates after 100 times is for still having 93.5% and 91.8%.
Embodiment 5:
Take by weighing FeSO respectively
47H
2O 5.56g, NH
4H
2PO
42.30g and LiOHH
2O 0.84g places ball grinder, does dispersant with ethanol, ball milling 2h, and the slurry behind the ball milling places Ar/H at 60 ℃ of dry down back ball milling powdereds
2(Ar accounts for 95V%, H
2Account for 5V%) 350 ℃ of following pre-burning 8h in the mixed gas protected high temperature process furnances, be cooled to room temperature.The pre-burning product is ground, the compressing tablet granulation is placed on Ar/H then again
2(Ar accounts for 95V%, H
2Account for 5V%) in the high temperature process furnances of mixed atmosphere, at 700 ℃ of roasting 15h.After being chilled to room temperature, grind, obtain LiFePO
4Positive electrode.Then with 96wt.%LiFePO
4And 4wt.%NbS
2High-energy ball milling 2h, the 1h that under 200 ℃ of temperature, anneals in the tube furnace of Ar atmosphere obtains LiFePO
4-NbS
2Mixed conductor compound (MCM).
The conductance of compound front and back is from 10
-7S/cm brings up to 10
-2The S/cm order of magnitude, the lithium ion diffusion rate is by 10 of pure phase
-14Cm/s
2Rise to 10
-12Cm/s
2The order of magnitude, tap density are 1.5g/cm
3The electrochemical property test method of gained sample such as instance 1, LiFePO
4-NbS
2MCM discharges and recharges under 1C and 2C multiplying power, and first discharge specific capacity is respectively 143.5 and 130.4mAh/g, and the capability retention that circulates after 100 times is for still having 92.1% and 90.0%.
Embodiment 6:
Take by weighing FeSO respectively
47H
2O 8.34g, NH
4H
2PO
43.45g and LiOHH
2O 1.26g places ball grinder, does dispersant with ethanol, ball milling 3h, and the slurry behind the ball milling places Ar/H at 60 ℃ of dry down back ball milling powdereds
2(Ar accounts for 95V%, H
2Account for 5V%) 350 ℃ of following pre-burning 8h in the mixed gas protected high temperature process furnances, be cooled to room temperature.The pre-burning product is ground, the compressing tablet granulation is placed on Ar/H then again
2(Ar accounts for 95V%, H
2Account for 5V%) in the high temperature process furnances of mixed atmosphere, at 700 ℃ of roasting 15h.After being chilled to room temperature, grind, obtain LiFePO
4Positive electrode.Then with 95wt.%LiFePO
4And 5wt.%TiS
2High-energy ball milling 2h, the 1h that under 300 ℃ of temperature, anneals in the tube furnace of Ar atmosphere obtains LiFePO
4-TiS
2Mixed conductor compound (MCM).
The conductance of compound front and back is from 10
-7S/cm brings up to 10
-2The S/cm order of magnitude, the lithium ion diffusion rate is by 10 of pure phase
-14Cm/s
2Rise to 10
-12Cm/s
2The order of magnitude, tap density are 1.2g/cm
3The electrochemical property test method of gained sample such as instance 1, LiFePO
4-TiS
2MCM discharges and recharges under 1C and 2C multiplying power, and first discharge specific capacity is respectively 138.5 and 127.4mAh/g, and the capability retention that circulates after 100 times is for still having 94.6% and 92.3%.
Claims (10)
1. LiFePO
4-MX
yThe mixed conductor composite materials is characterized in that: said LiFePO
4-MX
yThe mixed conductor compound comprises: LiFePO4 and account for transition metal oxide or the sulfide of LiFePO4 0.01%-50.00wt.%.
2. a kind of LiFePO according to claim 1
4-MX
yThe preparation method of mixed conductor composite materials is characterized in that:
(1) be Li: Fe: P=0.9-1.5 with mol ratio: 1: 1 Li source compound, phosphate compounds, Fe source compound and the reducing agent that accounts for the 0.01-50.00wt.% of Li source compound, phosphate compounds and Fe source compound gross mass join in the ball grinder; Add the organic dispersing agent that accounts for Li source compound, phosphate compounds, Fe source compound and reducing agent gross mass 1.00-30.00wt.%, be stirred into the LiFePO4 pasty material;
(2) the LiFePO4 pasty material is carried out drying after, ball milling obtains LiFePO4 precursor powder again;
(3) with LiFePO4 precursor powder, with 250-450 ℃ of pre-burning 4-8 hour, the cooling back was ground and is obtained the pre-burning product in protective atmosphere;
(4) with the granulation of pre-burning product compressing tablet, in protective atmosphere in 450-950 ℃ of sintering 5-25 hour, grind after the cooling lithium iron phosphate positive material;
(5) with the oxide or the sulfide high-energy ball milling 1-8h of lithium iron phosphate positive material and transition metal, obtain mixture; Wherein the consumption of the oxide of transition metal or sulfide is the 0.01%-50.00wt.% of LiFePO4.
(6) with mixture, 100-400 ℃ of annealing 1-12h obtains LiFePO under protective atmosphere
4-MX
yThe mixed conductor composite materials.
3. a kind of LiFePO according to claim 2
4-MX
yThe preparation method of mixed conductor composite materials is characterized in that: said Li source compound is one or more in lithium carbonate, lithium nitrate, lithium acetate or the lithium hydroxide.
4. a kind of LiFePO according to claim 2
4-MX
yThe preparation method of mixed conductor composite materials is characterized in that: said Fe source compound is a ferrous sulfate, one or more in ferrous nitrate, ferrous oxalate, ferric acetate, ferric phosphate, iron oxide, ferric nitrate or the iron chloride.
5. a kind of LiFePO according to claim 2
4-MX
yThe preparation method of mixed conductor composite materials is characterized in that: said phosphate radical source compound is one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate or the phosphoric acid.
6. a kind of LiFePO according to claim 2
4-MX
yThe preparation method of mixed conductor composite materials is characterized in that: said reducing agent is one or more in sucrose, glucose, caramel, citric acid, oxalic acid, tartaric acid or the polyethylene glycol etc.
7. a kind of LiFePO according to claim 2
4-MX
yThe preparation method of mixed conductor composite materials is characterized in that: said organic dispersing agent is one or more the mixture in ethanol, methyl alcohol, n-butanol, propyl alcohol, acetone or the deionized water etc.
8. a kind of LiFePO according to claim 2
4-MX
yThe preparation method of mixed conductor composite materials is characterized in that: said transition metal oxide is Nd
2O
5, Co
3O
4, V
2O
5, MoO
3, V
2O
3, WO
2, MnO
2, CeO
2, TiO
2, among NiO, CoO or CuO etc. one or more.
9. a kind of LiFePO according to claim 2
4-MX
yThe preparation method of mixed conductor composite materials is characterized in that: said transient metal sulfide is NbS
2, TiS
2, WS
2, MoS
2, FeS
2, NiS
2, ZnS
2, TeS
2Or CoS
2In one or more.
10. a kind of LiFePO according to claim 2
4-MX
yThe preparation method of mixed conductor composite materials is characterized in that: said protective atmosphere is nitrogen, argon gas, nitrogen and hydrogen mixed gas, and wherein nitrogen accounts for 80-99V%, and hydrogen accounts for 1-20V%; Or argon gas and hydrogen mixed gas, wherein argon gas accounts for 80-99V%, and hydrogen accounts for 1-20V%.
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| CN103531792A (en) * | 2012-07-02 | 2014-01-22 | 喻维杰 | Manufacturing method of high-property lithium salt composite-phase lithium iron phosphate material |
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| CN106450302A (en) * | 2016-11-04 | 2017-02-22 | 成都新柯力化工科技有限公司 | Lithium ferric manganese phosphate-tungsten disulfide nanometer lithium cell positive material and preparation method thereof |
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