CN106784724A - A kind of LiFePO4The solvent heat assistant preparation method of@C/rGO multistage composite microballoons - Google Patents

A kind of LiFePO4The solvent heat assistant preparation method of@C/rGO multistage composite microballoons Download PDF

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CN106784724A
CN106784724A CN201710022278.2A CN201710022278A CN106784724A CN 106784724 A CN106784724 A CN 106784724A CN 201710022278 A CN201710022278 A CN 201710022278A CN 106784724 A CN106784724 A CN 106784724A
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lifepo
rgo
multistage composite
lithium
solvent heat
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CN106784724B (en
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张宗弢
王洪宾
王润伟
刘丽佳
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Jilin University
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/625—Carbon or graphite
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    • H01—ELECTRIC ELEMENTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

A kind of LiFePO4The solvent heat assistant preparation method of@C/rGO multistage composite microballoons, belongs to electrochemical energy storage materials technical field.The present invention is with trivalent Fe3+Salt is source of iron, by the hot method fabricated in situ resorcinol formaldehyde resin (RF) of a step mixed solvent and the LiFePO of graphene oxide (GO) dual modification4OH multistage composite microballoons LiFePO4OH@RF/GO.By complex microsphere, in the case where gas is protected, high temperature carbon thermal reduction treatment can be further converted to the LiFePO of redox graphene (rGO) modification4/ C multistage composite microballoons LiFePO4@C/rGO, it not only has up to~1.3g cm‑3Tap density, the primary particle of its nanoscale ensure that the electrode/electrolyte active contact area of abundance simultaneously, in addition the large area rGO nanometer sheets for loading significantly improve the electronic conductivity between microballoon inside and microballoon, material is showed excellent electrochemical lithium storage performance, have potential application prospect in high-energy/power lithium ion cells field.

Description

A kind of LiFePO4The solvent heat assistant preparation method of@C/rGO multistage composite microballoons
Technical field
The invention belongs to electrochemical energy storage materials technical field, and in particular to a kind of LiFePO4@C/rGO multistage composites are micro- The solvent heat assistant preparation method of ball.
Background technology
With energy-saving and emission-reduction and the increasingly lifting of environmental protection concept, people gradually recognize to develop the novel green vehicles The importance of (such as pure electric vehicle and hybrid-power electric vehicle), at the same time the performance indications for large-sized power battery it is also proposed that Technical requirements higher.Compared with the early stage battery such as plumbic acid, NI-G, Ni-MH battery, lithium ion battery (LIBs) has many Aspect technical advantage：Monomer output voltage is high, power/energy density is big, self discharge efficiency is low, have extended cycle life, environment-friendly One of and memory-less effect etc., therefore be considered as the first-selected power supply of large-scale industrialization powered vehicle.Positive electrode is One of core component of LIBs, its performance largely affects output voltage, energy density and security of battery etc., In addition cost accounts for more than the 30% of whole battery cost, and exploration and the exploitation about positive electrode are always important LIBs fields Research topic.Olivine LiMPO was found first from Goodenough seminars in 19974(M=Fe, Mn, Co, Ni) can be used as Since LIBs positive electrodes, olivine-type electrode material is increasingly becoming the focus that academia and industrial quarters are discussed warmly extensively.In recent years Come, iron-based positive electrode (LiFePO4) development it is very fast, and part have been realized in commercially producing and apply.With it Its Co, Ni base anode material is compared, LiFePO4Advantage be abundant, environment-friendly, cheap resource reserve, while also With steady (the 3.45V vs.Li/Li of output voltage+), reversible specific capacity (170mAh g high-1), have extended cycle life and safety Reliable the advantages of.But LiFePO4Material there is also some shortcoming and defect：Compared to LiCoO2And LiMn2O4Deng metal oxide Positive electrode, LiFePO4Intrinsic conductivity (<10-9S cm-1) and ion diffusion rates (10-12~10-14cm2s-1) relatively low, If therefore cannot be applied in the relatively harsh electrokinetic cell of technical requirements without modification.At present, relevant LiFePO4 The Optimized Measures of material are concentrated mainly on material with carbon-coated surface, body phase element doping and size and shape control aspect.Wherein, will Material with carbon-coated surface is combined with nano modification treatment and can not only lift LiFePO4Electronics between grain surface and crystal grain is led Electric rate, while Li can also effectively be shortened+Diffusion length of the ion in electrode material, and increase the work between material and electrolyte Property contact area, therefore be considered as improve LiFePO4One of ideal approach of chemical property.Regrettably, LiFePO4The tap density of@C nano composites often deficiency~1.0g cm-3, it is impossible to electrokinetic cell is met for volume high The demand of energy density.By contrast, LiFePO4@C multistage microballoons have good Packing character and mobility, under nature Tend to closely uniform accumulation, therefore its tap density is higher, and micro-nano multi-level structure ensure that material in chemical property Aspect is close to nano material.Additionally, microballoon pattern also possesses more superior processability in actual cell production process Energy.The hot method of hydrothermal/solvent is synthesis LiFePO4The common methods of@C multistage microballoons.Conventional hydrothermal/solvent-thermal process technique is most Using expensive and active divalence Fe2+Salt is used as source of iron, while needing extra addition reducing agent or filling protection gas to avoid Fe2 +Ion oxidation during the course of the reaction, and also need to experience secondary carbon coating step sometimes, these additional process are virtually being carried The high production cost and process complexity of material, therefore be not suitable for large-scale promotion popularization.
The content of the invention
It is an object of the invention to be directed to the problems of above-mentioned prior art and defect, there is provided a kind of simple, economy, Efficient LiFePO4The solvent heat assisted synthesizing method of@C/rGO multistage composite microballoons.
We are with trivalent Fe in the present invention3+Salt is source of iron, by the hot method fabricated in situ resorcinol-first of a step mixed solvent Urea formaldehyde (RF) and the LiFePO of graphene oxide (GO) dual modification4OH multistage composites microballoon (i.e. with RF as shell, LiFePO4OH is the LiFePO of kernel4OH@RF nano-particles agglomerate into multistage microballoon each other, and its Surface coating has large area GO nanometer sheets), labeled as LiFePO4OH@RF/GO.By LiFePO4OH RF/GO high temperature carbon thermal reduction treatment under protective atmosphere The LiFePO of redox graphene (rGO) modification can be further converted to4@C multistage composites microballoon (i.e. with carbon as shell, LiFePO4It is the LiFePO of kernel4@C nanos particle agglomerates into multistage microballoon each other, and its Surface coating has large area rGO to receive Rice piece), labeled as LiFePO4@C/rGO, its process need not additionally introduce carbon source or milled processed.LiFePO4@C/rGO are multistage Complex microsphere not only has up to 1.3g cm-3Tap density, while the LiFePO of its nanoscale4@C primary particles ensure Sufficient electrode/electrolyte active contact area, the rGO nanometer sheets for loading in addition can significantly lift microballoon inside and microballoon Between electronic conductivity, material is showed excellent electrochemical lithium storage performance, in high-energy/power lithium ion cells field There is potential application prospect.
To reach above-mentioned purpose, the present invention provides a kind of LiFePO4The preparation method of@C/rGO multistage composite microballoons, its step It is rapid as follows：
(1) phosphorus source, lithium source, source of iron and resorcinol are added sequentially in graphene oxide (GO) aqueous solution, fully Stir；
(2) formalin (quality of formaldehyde point in formalin is included to being added in step (1) gained mixed solution Number for 35~alcoholic solution 40%), stir；
(3) mixed solution obtained by step (2) is transferred in reactor, closed, thermostatic crystallization at autogenous pressures；Treat After reaction terminates and is cooled to room temperature, the precipitated product that solvent thermal process is formed is carried out into suction filtration, deionized water washing, dry successively Dry treatment obtains LiFePO4OH@RF/GO powder precursors；
(4) by step (3) gained LiFePO4OH@RF/GO powder precursors carry out high-temperature calcination treatment under protective atmosphere Obtain LiFePO of the present invention4@C/rGO multistage composite microballoons.
Wherein, the mol ratio between phosphorus source, lithium source, source of iron, resorcinol (R) component is P：Li：Fe：R=1：1~6.0： 0.25~3.0：0.05~5.0, preferably P：Li：Fe：R=1：1.05~3.0：0.75~1.2：0.2~3.0；Resorcinol It is 0.05~3.0 with the mol ratio of formaldehyde：1, preferably 0.25~1.5：1；Graphene oxide (GO) addition is LiFePO4OH 0.01~20wt.% of theoretical yield, preferably 0.5~10wt.%.
In step (1), phosphorus source is in phosphoric acid, ammonium dihydrogen phosphate, DAP, ammonium phosphate, lithium dihydrogen phosphate One or more, preferably phosphoric acid, ammonium dihydrogen phosphate.
In step (1), the lithium source is lithium hydroxide, lithium acetate, lithium oxalate, lithium nitrate, lithium carbonate, lithium chloride, oxidation One or more in lithium, preferably lithium hydroxide, lithium acetate.
In step (1), the source of iron be ferric nitrate, iron chloride, ferric sulfate, ammonium ferric sulfate, ironic citrate in one kind or It is various, preferably ferric nitrate, ferric sulfate.
Described that phosphorus source is added in graphene oxide (GO) aqueous solution in step (1), the molar concentration of phosphorus source is 0.02 ~10mol L-1, preferably 0.25~3mol L-1。
In step (2), the alcoholic solution is methyl alcohol, ethanol, isopropanol, 1,3-PD, ethylene glycol, glycerine, four sweet One or more in alcohol, polyethylene glycol, preferably methyl alcohol.
In step (2), in the mixed solution that the step (2) obtains, H2Matter in O components and alcoholic solution between alkoxide component Amount is than being 0.05~20：1, preferably 0.25~5：1.
In step (3), the crystallization temperature is 70~350 DEG C, and preferably 120~250 DEG C, the crystallization time is 0.1~96h, preferably 1~24h.
In step (3), stir speed (S.S.) during the thermostatic crystallization is 0~3000rpm, preferably 150~ 1200rpm。
In step (3), the dried process temperature is -80~120 DEG C, preferably 45~90 DEG C；The dried process time is 0.1~72h, preferably 3~24h.
In step (4), the calcining heat is 400~850 DEG C, preferably 500~750 DEG C；Calcination time be 0.2~ 24h, preferably 3~12h；Heating rate is 0.1~30 DEG C of min-1, preferably 1~5 DEG C min-1。
In step (4), the protective atmosphere is the one kind or many in nitrogen, argon gas, nitrogen-hydrogen gaseous mixture, argon-hydrogen gaseous mixture Plant, preferably argon gas, argon-hydrogen gaseous mixture.
Relative to prior art, the present invention has following characteristics and beneficial effect：
(1) present invention is with trivalent Fe3+Salt is source of iron, by the hot method fabricated in situ resorcinol-formaldehyde of a step mixed solvent Resin (RF) and the LiFePO of graphene oxide (GO) dual modification4OH multistage composite microballoons, labeled as LiFePO4OH@RF/GO。 By LiFePO4OH RF/GO high temperature carbon thermal reduction treatment in the case where gas is protected can be further transformed to redox graphene (rGO) The LiFePO of modification4@C multistage composite microballoons, labeled as LiFePO4@C/rGO, its process need not additionally introduce carbon source or grinding Mixed processing, is a kind of economic, efficient, environmentally friendly synthesis method, is expected to realize large-scale commercial production.
(2) LiFePO prepared by the present invention4@C/rGO multistage composites microballoon not only has up to~1.3g cm-3Jolt ramming Density, while the LiFePO of its nanoscale4@C primary particles ensure that active contact face sufficient between electrode and electrolyte Product, the rGO nanometer sheets for loading in addition can significantly lift the electronic conductivity between microballoon inside and microballoon, show material Excellent electrochemical lithium storage performance, in high-energy/power lithium ion cells field, (such as electrokinetic cell, large-scale energy-accumulating power station) has Potential application prospect.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of sample prepared by embodiment 1.
Fig. 2 is sample (A) low power prepared by embodiment 1 and (B) high power ESEM (SEM) photo.
Fig. 3 is constant current charge-discharge curve of the sample prepared by embodiment 1 under half-cell system.
Specific embodiment
The present invention is made with reference to following instance being further described, but the scope of protection of present invention is not limited to reality Apply the scope of example statement.
Embodiment 1
(1) by 1.153g H3PO4The aqueous solution (H3PO4Mass fraction for 85%), 0.84g LiOHH2O, 4.04g Fe (NO3)3·9H2O and 0.55g resorcinols sequentially add 10g, concentration for 2.0mg mL-1Graphene oxide (GO) aqueous solution In, stir；
(2) (mass fraction of formaldehyde is to add 10g to include 0.81g formalins in the solution for obtaining to step (1) 37%) methanol solution, stirs；
(3) step (2) mixed solution is transferred in reactor, closed, 180 DEG C of constant temperature stirrings at autogenous pressures (600rpm) crystallization 6h.After completion of the reaction, product is carried out into suction filtration, deionized water washing, and the forced air drying in 70 DEG C of baking ovens 12h obtains LiFePO4OH@RF/GO powder precursors；
(4) by the LiFePO obtained by step (3)4OH@RF/GO powder precursors are placed in Ar/H2(H2Volume fraction be 6%) in the tube furnace of atmosphere, with 2 DEG C of min-1Heating rate rise to 700 DEG C and constant temperature and keep 6h to obtain final product LiFePO4@C/rGO Multistage composite microballoon, its quality about 1.2g.
Embodiment 2
(1) by 1.153g H3PO4The aqueous solution (H3PO4Mass fraction for 85%), 0.84g LiOHH2O, 4.04g Fe (NO3)3·9H2O and 0.66g resorcinols sequentially add 10g, concentration for 5.0mg mL-1Graphene oxide (GO) aqueous solution In, stir；
(2) 1.215g formalins are included to addition 10mL in step (1) solution (mass fraction of formaldehyde is 37%) Methanol solution, stir；
(3) step (2) mixed solution is transferred in reactor, closed, 170 DEG C of constant temperature stirrings at autogenous pressures (450rpm) crystallization 8h.After completion of the reaction, product is carried out into suction filtration, deionized water washing, and the forced air drying in 80 DEG C of baking ovens 10h obtains LiFePO4OH@RF/GO powder precursors；
(4) by the LiFePO obtained by step (3)4OH@RF/GO powder precursors are placed in Ar/H2(H2Volume fraction be 6%) in the tube furnace of atmosphere, with 2 DEG C of min-1Heating rate rise to 700 DEG C and constant temperature and keep 8h to obtain final product LiFePO4@C/rGO Multistage composite microballoon, its quality about 1.25g.
Embodiment 3
(1) by 1.153g H3PO4The aqueous solution (H3PO4Mass fraction be 85wt.%), 1.53g CH3COOLi·2H2O, 4.04g Fe(NO3)3·9H2O and 0.55g resorcinols sequentially add 10g, concentration for 3.0mg mL-1Graphene oxide (GO) In the aqueous solution, stir；
(2) to adding 10g to include 1.215g formalins in step (1) solution, (mass fraction of formaldehyde is Methanol solution 37wt.%), stirs；
(3) step (2) mixed solution is transferred in reactor, closed, 200 DEG C of constant temperature stirrings at autogenous pressures (600rpm) crystallization 5h.After completion of the reaction, product is carried out into suction filtration, deionized water washing, and the forced air drying in 80 DEG C of baking ovens 12h obtains LiFePO4OH@RF/GO powder precursors；
(4) by the LiFePO obtained by step (3)4OH@RF/GO powder precursors are placed in the tube furnace of Ar atmosphere, with 3 DEG C min-1Speed be warming up to 650 DEG C and constant temperature and keep 10h to obtain final product LiFePO4@C/rGO multistage composite microballoons, its quality about 1.2g.
The LiFePO prepared to embodiment 14@C/rGO multistage composites microballoons carry out structure and performance evaluation.
Thing phase phenetic analysis are carried out to sample using Rigaku D/MAX-2550 types X-ray diffractometer (Japan), as a result such as Shown in Fig. 1.Analyzed through comparing, XRD spectra and the olivine LiFePO of sample4Standard spectrogram fits like a glove, miscellaneous in the absence of other Peak, active component is LiFePO in illustrating sample4Pure phase.Additionally, towering diffraction peak shape shows that the crystallinity of sample is good.
Morphology characterization is carried out to sample using JEOL JSM-6700F types SEM (Japan), as a result such as Fig. 2 It is shown.Low power SEM photograph (Fig. 2A) display sample be rendered as regular microballoon pattern, diameter between 2~3 μm, microballoon table Face is attached with the rGO nanometer sheets of large area, and these nanometer sheets are by neighbouring LiFePO4@C microballoons bridging each other, effectively improves Electronics continuity between microballoon.High power SEM photograph (Fig. 2 B) further demonstrates that LiFePO4@C microballoons have typical multilevel hierarchy Characteristic, by a large amount of LiFePO4@C nanos particle (~65nm) are piled up and are formed, and rGO nanometer sheets are firmly adhered to LiFePO in addition4@ C microsphere surfaces and part be embedded in inside microballoon, form continuous three-dimensional conductive network from the inside to the outside.
Electrochemical lithium storage performance characterization is carried out to sample using Wuhan LAND CT2001A types battery test system (China), Result is as shown in Figure 3.(with the product of embodiment 1 as positive pole, metal lithium sheet is negative pole, and Celgard 2400 gathers under half-cell system Propylene film is barrier film, and electrolyte uses traditional LiPF6Base organic electrolyte) constant current charge-discharge as shown by data sample have it is excellent Different electrochemical lithium storage performance：(0.2C, the 1C=170mA g under low range-1), sample can release 157.2mAh g-1Can Inverse specific capacity, and the platform properties of charging and discharging curve are good；When multiplying power is promoted to 1C, 2C, 5C and 10C, its specific discharge capacity It is kept at 146.7,137.7,123.6 and 109.4mAh g-1；Even if under 30C and 60C high magnifications, the reversible ratio of sample Capacity is still up to 86.5 and 60.8mAh g respectively-1。
The above, is only several case study on implementation of the invention, and any formal limitation is not done to the present invention, Protection scope of the present invention not limited to this.

Claims (10)

1. a kind of LiFePO4The solvent heat assistant preparation method of@C/rGO multistage composite microballoons, its step is as follows：
(1) phosphorus source, lithium source, source of iron and resorcinol are added sequentially in the graphene oxide GO aqueous solution, are sufficiently stirred for It is even；
(2) alcoholic solution of formalin is included to addition in step (1) gained mixed solution, is stirred；
(3) mixed solution obtained by step (2) is transferred in reactor, closed, thermostatic crystallization at autogenous pressures；Question response After terminating and being cooled to room temperature, the precipitated product that solvent thermal process is formed is carried out suction filtration, deionized water washing, dried successively at Reason obtains LiFePO4OH@RF/GO powder precursors；
(4) by step (3) gained LiFePO4OH@RF/GO powder precursors carry out high-temperature calcination treatment under protective atmosphere and obtain final product LiFePO of the present invention4@C/rGO multistage composite microballoons；
Wherein, the mol ratio between phosphorus source, lithium source, source of iron, resorcinol component is P：Li：Fe：R=1：1~6.0：0.25~ 3.0：0.05~5.0, R represent resorcinol；Resorcinol is 0.05~3.0 with the mol ratio of formaldehyde：1, graphene oxide GO Addition is LiFePO40.01~20wt.% of OH theoretical yields, in formalin the mass fraction of formaldehyde be 35~ 40%.
2. a kind of LiFePO as claimed in claim 14The solvent heat assistant preparation method of@C/rGO multistage composite microballoons, it is special Levy and be：In step (1), phosphorus source is in phosphoric acid, ammonium dihydrogen phosphate, DAP, ammonium phosphate, lithium dihydrogen phosphate Plant or various.
3. a kind of LiFePO as claimed in claim 14The solvent heat assistant preparation method of@C/rGO multistage composite microballoons, it is special Levy and be：In step (1), the lithium source is lithium hydroxide, lithium acetate, lithium oxalate, lithium nitrate, lithium carbonate, lithium chloride, lithia In one or more.
4. a kind of LiFePO as claimed in claim 14The solvent heat assistant preparation method of@C/rGO multistage composite microballoons, it is special Levy and be：In step (1), the source of iron is the one kind or many in ferric nitrate, iron chloride, ferric sulfate, ammonium ferric sulfate, ironic citrate Kind.
5. a kind of LiFePO as claimed in claim 14The solvent heat assistant preparation method of@C/rGO multistage composite microballoons, it is special Levy and be：It is described that phosphorus source is added in the graphene oxide GO aqueous solution in step (1), the molar concentration of phosphorus source for 0.02~ 10mol L-1。
6. a kind of LiFePO as claimed in claim 14The solvent heat assistant preparation method of@C/rGO multistage composite microballoons, it is special Levy and be：In step (2), the alcoholic solution is methyl alcohol, ethanol, isopropanol, 1,3-PD, ethylene glycol, glycerine, four sweet One or more in alcohol, polyethylene glycol.
7. a kind of LiFePO as claimed in claim 14The solvent heat assistant preparation method of@C/rGO multistage composite microballoons, it is special Levy and be：In the mixed solution that the step (2) obtains, H2Mass ratio in O components and alcoholic solution between alkoxide component is 0.05 ~20：1.
8. a kind of LiFePO as claimed in claim 14The solvent heat assistant preparation method of@C/rGO multistage composite microballoons, it is special Levy and be：In step (3), the crystallization temperature is 70~350 DEG C, and the crystallization time is 0.1~96, thermostatic crystallization mistake The stir speed (S.S.) of journey is 0~3000rpm, and dried process temperature is -80~120 DEG C, and the dried process time is 0.1~72h.
9. a kind of LiFePO as claimed in claim 14The solvent heat assistant preparation method of@C/rGO multistage composite microballoons, it is special Levy and be：In step (4), the calcining heat be 400~850 DEG C, calcination time be 0.2~24h, heating rate be 0.1~ 30℃ min-1。
10. a kind of LiFePO as claimed in claim 14The solvent heat assistant preparation method of@C/rGO multistage composite microballoons, it is special Levy and be：In step (4), the protective atmosphere is the one kind or many in nitrogen, argon gas, nitrogen-hydrogen gaseous mixture, argon-hydrogen gaseous mixture Kind.
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Cited By (3)

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CN108448105A (en) * 2018-05-16 2018-08-24 苏州大学 A kind of preparation method of lithium ion battery anode material lithium iron phosphate/redox graphene
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