Lithium iron phosphate positive material of a kind of doped graphene and preparation method thereof
Technical field
The present invention relates to lithium ion cell electrode preparing technical field, be specifically related to lithium iron phosphate positive material of a kind of doped graphene and preparation method thereof.
Background technology
As the LiFePO4 (LiFePO of anode material for lithium-ion batteries
4), also known as LFP, have the stable charge and discharge platform of 3.4V, up to the theoretical capacity of 170mAh/g, and it is cheap, be easy to preparation, environmentally friendly, safety, the advantage such as cycle performance and good thermal stability.These advantages make LiFePO4 be considered to the power battery anode material of great potential, extremely the concern of people.But because the structural factor of LiFePO4 self causes its conductivity, on the low side (electronic conductivity is 10
-10~ 10
-9s/cm), significantly limit chemical property and the application of LiFePO4.Current people are by the conductivity of means all significantly the improve LiFePO4 such as element doping, carbon is coated, the high volence metal ions such as divalence magnesium, trivalent aluminium, nickelous and the divalence of such as adulterating in iron lithium phosphate material is violent, or at particle surface coated with conductive carbon-coating etc.But on the one hand because carbon material surface complex structure, interface resistance are comparatively large, when rate charge-discharge, capacity can decline significantly; On the other hand the carbon of general technology loosens due to quality, and it is loose to distribute between LiFePO4, seriously reduces the tap density of LiFePO 4 material, thus have impact on the compacted density of pole piece.Therefore, reduce the carbon content in positive electrode, do not reduce again conductivity and the cycle performance of material, be current lithium iron phosphate positive material problem demanding prompt solution simultaneously as far as possible.
Graphene (Graphene) is the carbon atomic layer of monoatomic thickness, is that carbon atom is with sp
2the thickness that hydbridized carbon atoms is formed is only the individual layer two dimensional crystal being arranged in honeycomb lattice (honeycombcrystallattice) of the hexaplanar of individual layer atom.Graphene has extremely excellent conductivity and huge specific area, can material modified as LiFePO4.
CN101800310A discloses a kind of preparation method of graphene-doped anode material for lithium-ion batteries, wherein the main component of positive electrode is lithium iron phosphate nano particle, its process, for directly to be mixed with Graphene by lithium iron phosphate nano particle, prepares Graphene/lithium iron phosphate positive material by solid phase method.It comprises particularly: prepare Graphene, graphene oxide, intercalated graphite alkene first respectively, then Graphene, graphene oxide, intercalated graphite alkene compound are mixed in the synthesis material of lithium iron phosphate nano particle, or after preparing lithium iron phosphate nano particle, the Graphene of lithium iron phosphate nano particle and intercalated graphite alkene, graphene oxide or electronation is directly mixed, drying, filtration, washing, drier and annealing in process, the material of the bridging of synthesizing graphite alkene, graphene oxide or coated LiFePO 4 for lithium ion batteries nano particle structure form.The lithium iron phosphate nano particle that the method is obtained, can improve electron conduction ability greatly through performance characterization, and the application for lithium ion battery provides that a kind of processing technology is simple, with low cost, capacity is high and the lithium ion cell positive material of safety.But the LiFePO4/graphene anode material of the method Solid phase synthesis is difficult to make LiFePO4 fully mix with Graphene, seriously reduces the utilance of graphenic surface, thus adds the internal resistance of lithium battery, limits the power density of lithium battery.
CN101752561A discloses a kind of preparation method of Graphene modified phosphate iron lithium positive electrode active materials and the lithium rechargeable battery based on this positive electrode active materials, be characterized in adopting the graphene nanometer sheet of sandwich construction as conductive modified material, detailed process is: described positive electrode active materials is scattered in the aqueous solution by Graphene or graphene oxide and LiFePO4, by stirring and ultrasonicly making its Homogeneous phase mixing, the dry LiFePO 4 material obtaining Graphene or graphene oxide compound subsequently, the lithium iron phosphate anode active material of Graphene modification is finally obtained again by high annealing.Have compared with the modified lithium battery such as and conducting polymer doping coated with traditional carbon based on the lithium rechargeable battery of this positive electrode active materials that battery capacity is high, impulse electricity cycle performance is excellent, the life-span long and the feature of high cyclical stability, but the specific area of this graphene nanometer sheet is lower (is less than 1000m
2/ g), and the space between nanometer sheet is difficult to form effective passage, limits the free diffusing of lithium ion in electrolyte.
How Graphene and LiFePO4 are effectively mixed in prior art, both made full use of the Graphene of Large ratio surface, do not affect again the capacity of LiFePO 4 material when rate charge-discharge and tap density becomes a lithium iron phosphate positive material problem demanding prompt solution.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is the preparation method of the lithium iron phosphate positive material providing a kind of doped graphene, and described method comprises: soluble lithium compounds, phosphate and ferrous salt are mixed in dispersant and obtain dispersion liquid a by (1); (2) be oxidized in concentrated acid environment by Graphene derived material and obtain graphene oxide derived material, then ultrasonic disperse is in dispersion liquid, obtains dispersion liquid b; (3) dispersion liquid a and dispersion liquid b is mixed to get dispersion liquid c, stirs, spray-dried, calcining, obtains the lithium iron phosphate positive material of doped graphene.
As optimal technical scheme, step (1) obtains dispersion liquid a for soluble lithium compounds, phosphate and ferrous salt being mixed in dispersant by atomic ratio Li: Fe: P=3: 1: 1; Described dispersant is ethanol and/or water, preferred deionized water.
Described soluble lithium compounds is selected from the combination of in lithium hydroxide, lithium nitrate, lithium acetate, lithium carbonate a kind or at least 2 kinds, the combination etc. of the combination of such as lithium acetate, lithium carbonate, lithium hydroxide/lithium nitrate, the combination of lithium carbonate/lithium nitrate, lithium hydroxide/lithium carbonate/lithium nitrate, preferred lithium nitrate and/or lithium carbonate.
Described ferrous salt is selected from the combination of in ferrous sulfate, ferrous acetate, frerrous chloride, ferrous nitrate a kind or at least 2 kinds, such as ferrous sulfate, ferrous nitrate, ferrous acetate the combination of frerrous chloride, ferrous nitrate the combination of frerrous chloride, ferrous sulfate ferrous nitrate the combination etc. of frerrous chloride, preferred frerrous chloride and/or ferrous nitrate.
Described phosphate is selected from phosphoric acid dihydro amine, diammonium hydrogen phosphate, a kind of ferrous ammonium phosphate or the combination of at least 2 kinds, such as phosphoric acid dihydro amine, ferrous ammonium phosphate, phosphoric acid dihydro amine the combination etc. of diammonium hydrogen phosphate, preferably phosphoric acid diammonium hydrogen.
Described in step (1), mixing is without particular/special requirement, and the hybrid mode that any one those skilled in the art can be known all can realize the present invention, such as, stir, concussion etc.
As optimal technical scheme, described in step (2), Graphene is Graphene derived material, preferred three-dimensional, surface have Graphene derived material nanometer level microporous in a large number, and the conductance of further preferably Graphene derived material is greater than 100mS/m and/or its pore diameter range is 2nm-100nm.
What those skilled in the art can be known can prepare surface has the method for Graphene derived material nanometer level microporous in a large number all to can be used in the present invention, and especially can prepare conductance and be greater than 100mS/m and/or surface and have a large amount of pore diameter range to be the method for the Graphene derived material of the micropore of 2nm-100nm.Such as CN102070140A discloses a kind of method utilizing highly basic process to obtain preparing high-specific surface area graphene material, utilize the reaction at high temperature of highly basic and carbon, the graphene powder that heat treatment or microwave irradiation obtain carries out further chemical treatment, thus fast, the large batch of micropore eroding away nanometer scale at graphenic surface, greatly improve its specific area, and high-temperature process can reduced graphene further, thus ensure obtain the high conductivity of material.The Graphene derived material of the three-dimensional that this patent system obtains, porous, specific area is up to 1500m
2/ g ~ 3000m
2/ g, also keeps the high conductance of material simultaneously.Porous method disclosed in patent CN102070140A prepared, the Graphene derived material of three-dimensional structure is used for the present invention can make in positive electrode, LiFePO4 fully mixes with Graphene, and the utilance of graphenic surface can be improved, reduce the resistance of electrode slice.
In step (2), described concentrated acid is selected from the combination of in the concentrated sulfuric acid, red fuming nitric acid (RFNA), dense perchloric acid, SPA and concentrated hydrochloric acid a kind or at least 2 kinds, the preferred concentrated sulfuric acid, concentrated hydrochloric acid, dense perchloric acid the combination of SPA, red fuming nitric acid (RFNA) dense perchloric acid combination, the preferred concentrated sulfuric acid and/or the dense perchloric acid of concentrated hydrochloric acid.
Described being oxidized to is oxidized with oxidant; The time of described oxidation is 0.5h-5h, such as 0.5h, 0.6h, 0.7h, 2h, 4h, 4.8h, 4.9h, 5h etc.; Described oxidant is selected from the combination of in potassium permanganate, nitrate, perchlorate, hydrogen peroxide, chromate and persulfate a kind or at least 2 kinds, such as potassium permanganate, sodium nitrate, potassium chromate, potassium peroxydisulfate, hydrogen peroxide, potassium permanganate the combination of sodium nitrate, sodium nitrate the combination of sodium peroxydisulfate, potassium permanganate potassium chromate the combination of potassium peroxydisulfate, a kind in preferably nitrate, chromate, persulfate or the combination of at least 2 kinds.
As optimal technical scheme, in dispersion liquid c described in step (3), the mass percentage that Graphene derived material accounts for dispersion liquid c is 0.1wt% ~ 10wt%, such as 0.11wt%, 0.12wt%, 3wt%, 5wt%, 8wt%, 9wt%, 9.8wt%, 9.9wt%, 10wt% etc.
Described spray-dired temperature is 100 DEG C-200 DEG C, such as 100 DEG C, 101 DEG C, 102 DEG C, 120 DEG C, 190 DEG C, 198 DEG C, 199 DEG C, 200 DEG C etc., preferably 120 DEG C-180 DEG C.
The temperature of described high-temperature calcination process is 500 DEG C-1200 DEG C, such as 500 DEG C, 510 DEG C, 520 DEG C, 800 DEG C, 1000 DEG C, 1100 DEG C, 1190 DEG C, 1200 DEG C etc., preferably 500 DEG C-1000 DEG C.
Described high-temperature calcination is preferably carried out under protective atmosphere; the gas componant of the technological know-how unrestricted choice protective atmosphere that those skilled in the art can grasp according to oneself; the preferred argon gas of the present invention, nitrogen or their mixing with hydrogen, particularly preferably calcine under an argon atmosphere.
As alternatives, the preparation method of the lithium iron phosphate positive material of described doped graphene comprises: lithium hydroxide, lithium nitrate, ferrous ammonium phosphate, ferrous sulfate are mixed to get dispersion liquid a by atomic ratio Li: Fe: P=3: 1: 1 by (1) in water; (2) by Graphene derived material in concentrated hydrochloric acid environment, add potassium permanganate and it be oxidized, obtain graphene oxide derived material, then through ultrasonic disperse in water, obtain dispersion liquid b; (3) dispersion liquid a and dispersion liquid b is mixed to get dispersion liquid c, stirs, calcine in spray-dried, nitrogen atmosphere, obtain the lithium iron phosphate positive material of doped graphene.
As optimal technical scheme, the preparation method of the lithium iron phosphate positive material of described doped graphene comprises: lithium nitrate, lithium carbonate, frerrous chloride, diammonium hydrogen phosphate are mixed to get dispersion liquid a by atomic ratio Li: Fe: P=3: 1: 1 by (1) in water; (2) by Graphene derived material in dense perchloric acid environment, add sodium nitrate and potassium peroxydisulfate is oxidized it, obtain graphene oxide derived material, then through ultrasonic disperse in water, obtain dispersion liquid b; (3) dispersion liquid a and dispersion liquid b is mixed to get dispersion liquid c, stirs, calcine in spray-dried, argon gas atmosphere, obtain the lithium iron phosphate positive material of doped graphene.
Two of object of the present invention is the lithium iron phosphate positive material providing a kind of doped graphene prepared by method of the present invention.
The lithium iron phosphate positive material of described doped graphene is that Graphene is put up a bridge or coated lithium iron phosphate positive material, and wherein Graphene has three-dimensional structure and surface has a large amount of nanometer level microporous.
Three of object of the present invention is the purposes of the lithium iron phosphate positive material providing a kind of doped graphene.
The lithium iron phosphate positive material of described doped graphene can be used for preparing lithium ion battery, especially can be used for the positive plate preparing lithium rechargeable battery, preparation-obtained lithium rechargeable battery, electrode slice has the network-like hole passage be interconnected, specific capacity is greater than 150mAh/g, and the typical but non-limiting purposes of the present invention prepares button lithium ion battery.
Four of object of the present invention is to provide a kind of lithium ion battery, and the lithium iron phosphate positive material of the doped graphene of positive electrode prepared by the present invention of described lithium ion battery is made.
The capacitance of described lithium ion battery can reach more than 150mAh/g, and tap density can reach 1.5g/cm
3above, cycle performance is excellent, and internal resistance is little, and the life-span is long.
Compared with prior art, the present invention has following beneficial effect:
Positive plate of lithium battery prepared by the lithium iron phosphate positive material of the doped graphene obtained by the present invention, many network-like aperture passage be interconnected are dispersed with in sheet, lithium-ion electrolyte fully freely can spread in these aperture passage, with the lithium rechargeable battery obtained by this material there is battery capacity high (being greater than 150mAh/g), cycle performance is excellent, tap density is large (can reach 1.5g/cm
3above), the advantage that internal resistance is little and the life-span is long.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of button lithium ion battery and the microstructure schematic diagram of LiFePO4/graphene composite material;
Fig. 2 is the X-ray diffracting spectrum of LiFePO4/graphene composite material that embodiment one obtains;
Fig. 3 is the button lithium ion battery 0.2C multiplying power first charge-discharge curve that embodiment one obtains;
Fig. 4 is the button lithium ion battery 0.2C multiplying power first charge-discharge curve that embodiment two obtains.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment one
1, the LiFePO 4 material of doped graphene is prepared:
(1) in the aqueous solution, add lithium hydroxide and lithium nitrate, phosphoric acid dihydro amine and ferrous sulfate and ferrous acetate by atomic ratio Li: Fe: P=3: 1: 1, form mixed solution.
(2) the three-dimensional derived material of 1.0g Graphene (its surface has a large amount of pore diameter range to be the micropore of 2nm-100nm) is taken, join in the 50ml concentrated sulfuric acid, 3.5g potassium permanganate is slowly added under stirring, stirring at room temperature reacts 0.5 hour, then 100ml deionized water is slowly added, drip hydrogen peroxide until do not have bubble to produce, filter and spend deionized water to neutral, drying obtains the three-dimensional derived material of graphene oxide.In the water-soluble solution of the three-dimensional derived material of the Graphene that drying is obtained, the ultrasonic three-dimensional derived material aqueous solution of Graphene obtaining stably dispersing.
(3) mixed solution obtained to step (1) adds the aqueous dispersions of the three-dimensional derived material of graphene oxide that step (2) obtains, and makes the content of Graphene 1%.By stirring with after ultrasonic mixing, this mixed system being carried out at 150 DEG C spraying dry and obtaining pressed powder.By gained pressed powder high-temperature calcination 6h under 700 DEG C of argon shields, graphene oxide derived material is reduced into Graphene derived material, obtains the LiFePO 4 material of phosphorus doping Graphene.
2, the physicochemical property of the LiFePO 4 material of doped graphene: conductance 10
-4s/cm (the conductance 10 of pure phase
-9s/cm); Tap density is 1.6g/cm
3.Fig. 2 is the X-ray diffracting spectrum of obtained LiFePO4/graphene composite material.Can find out in the raw material LiFePO4/graphene composite material of gained, LiFePO4 is the LiFePO4 of pure olivine-type rhombic system phase structure.
3, button battery is prepared: the LiFePO 4 material powder of doped graphene, conductive agent acetylene black and binding agent Kynoar are mixed be coated on aluminium foil on make positive plate at 8.5: 0.5: 1 in mass ratio.In argon gas atmosphere glove box, with lithium sheet for negative pole, Cegard2500 film is barrier film, and ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) are electrolyte, are assembled into button battery.
Under constant temperature, in 2.2V ~ 3.9V voltage range, constant current charge-discharge test is carried out to battery.Fig. 3 is obtained button lithium ion battery 0.2C multiplying power first charge-discharge curve.Gained composite ferric lithium phosphate material discharge voltage is about 3.4V as shown in Figure 3, and reversible capacity height is to 153mAh/g, and cycle performance of battery is also very superior.
Embodiment two
1, the LiFePO 4 material of doped graphene is prepared:
(1) in the aqueous solution, add lithium carbonate, lithium hydroxide and lithium acetate, ferrous ammonium phosphate, frerrous chloride and ferrous nitrate by atomic ratio Li: Fe: P=3: 1: 1, form mixed solution.
(2) the three-dimensional derived material (its conductance is greater than 100mS/m) of 5.0g Graphene is taken, join in the 100ml concentrated sulfuric acid, 17.5g potassium permanganate is slowly added under stirring, stirring at room temperature reacts 1.5 hours, then 300ml deionized water is slowly added, drip hydrogen peroxide until do not have bubble to produce, filter and spend deionized water to neutral, drying obtains the three-dimensional derived material of graphene oxide.In the water-soluble solution of the three-dimensional derived material of the Graphene that drying is obtained, the ultrasonic three-dimensional derived material aqueous solution of Graphene obtaining stably dispersing.
(3) mixed solution obtained to step (1) adds the three-dimensional derived material aqueous dispersions of Graphene that step (2) obtains, and makes the content of Graphene 5%.By stirring with after ultrasonic mixing, this mixed system spraying dry at 150 DEG C is obtained pressed powder.By the high-temperature calcination 6 hours under 1000 DEG C of argon shields of this powder, graphene oxide derived material is reduced into Graphene derived material, obtains the LiFePO 4 material of doped graphene.
2, the physicochemical property of the LiFePO 4 material of doped graphene: conductance 10
-4s/cm, and the conductance of pure phase is only 10
-9s/cm, composite material improves 5 orders of magnitude compared with the conductance of pure phase, and tap density is 1.7g/cm
3.Fig. 4 is obtained button lithium ion battery 0.2C multiplying power first charge-discharge curve.During products therefrom 0.2C rate charge-discharge, specific capacity height arrives 165mAh/g as shown in Figure 4.
Embodiment three
1, the LiFePO 4 material of doped graphene is prepared:
(1) in the aqueous solution, add lithium hydroxide and lithium nitrate, phosphoric acid dihydro amine and ferrous sulfate and ferrous acetate by atomic ratio Li: Fe: P=3: 1: 1, form mixed solution.
(2) the three-dimensional derived material (its conductance is greater than 100mS/m) of 1.0g Graphene is taken, join in the 50ml concentrated sulfuric acid, 4g potassium chromate is slowly added under stirring, stirring at room temperature reacts 5 hours, then 100ml deionized water is slowly added, drip hydrogen peroxide until do not have bubble to produce, filter and spend deionized water to neutral, drying obtains the three-dimensional derived material of graphene oxide.In the water-soluble solution of the three-dimensional derived material of the Graphene that drying is obtained, the ultrasonic three-dimensional derived material aqueous solution of Graphene obtaining stably dispersing.
(3) mixed solution obtained to step (1) adds the aqueous dispersions of the three-dimensional derived material of graphene oxide that step (2) obtains, and makes the content of Graphene 10%.By stirring with after ultrasonic mixing, this mixed system being carried out at 200 DEG C spraying dry means and obtaining pressed powder.By gained pressed powder high-temperature calcination 6h under 1200 DEG C of argon shields, graphene oxide derived material is reduced into Graphene derived material, obtains the LiFePO 4 material of phosphorus doping Graphene.
2, the physicochemical property of the LiFePO 4 material of doped graphene: conductance 10
-4s/cm (the conductance 10 of pure phase
-9s/cm); Tap density is 1.6g/cm
3, during products therefrom 0.2C rate charge-discharge, specific capacity is 158mAh/g.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.