CN103887492B - The three-dimensional complex spherical powder of nanostructured mangaic acid lithium/lithium iron phosphate/carbon material and preparation method thereof - Google Patents
The three-dimensional complex spherical powder of nanostructured mangaic acid lithium/lithium iron phosphate/carbon material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the three-dimensional complex spherical powder material of a kind of nanostructured mangaic acid lithium/lithium iron phosphate/carbon and preparation technology thereof, it is mainly by nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon three phase compositions, and spherical in shape, the particle diameter of material is micron order, the particle diameter of primary particle is nanoscale, and nano-grade lithium iron phosphate and carbon uniform deposition are in the microsphere surface and/or hole of nano-porous structure LiMn2O4. Preparation technology comprises: manganese salt and sodium oxalate are added in reactor, after fully stirring, the spherical manganese oxalate roasting under inert atmosphere obtaining is obtained to MnO2, then press proportioning by the MnO of respective quality2Powder, lithium salts, molysite, phosphate and carbon source are mixed, and fully react to obtain semi-finished product; Finally crystallization processing in the mixed atmosphere of nitrogen hydrogen, obtains finished product. Product of the present invention can improve stability and the electric conductivity of cell positive material, improves its chemical property.
Description
Technical field
The present invention relates to the preparing technical field of anode material for lithium-ion batteries, relate in particular to a kind of LiMn2O4/lithium iron phosphate/carbon threeDimension composite and preparation method thereof.
Background technology
Along with the expansion of new-energy automobile to electrokinetic cell demand, in the urgent need to develop high safety, high-energy-density, high power,Long circulation life, working range are wide, environmental protection and inexpensive positive electrode. With respect to positive pole material of lithium cobalt acid exist expensive price,The defects such as capacity room for promotion is extremely limited, resource scarcity, poor stability, it is suitable that LiMn2O4 has capacity as cell positive materialIn, the advantage such as average voltage is high, security good, cheap, raw material source is wide, synthetic easy, LiMn2O4 has become movingThe first-selection of power anode material for lithium-ion batteries. LiFePO 4 material is also the positive electrode that recent years, fast development was got up, its toolThere is cyclicity cheap, nontoxic, that security is higher, raw material sources are extensive, structural stability is better, capacity is high, superiorThe advantages such as energy, this makes it have broad application prospects at electrokinetic cell and stand-by power supply field. But, relatively LiMn2O4 andThe properties of lithium iron phosphate positive material finds, although that both have advantages of is outstanding separately, also has separately and significantly lacksFall into, as poor in LiMn2O4 cyclicity, when especially temperature is higher than 55 DEG C, capacity attenuation is fast especially; LiFePO4 tap density is low,Volume and capacity ratio is low, and ionic conductivity and electronic conductivity are less, and in the time of heavy-current discharge, capacity attenuation is very fast, especially low temperaturePoor performance is that it is applied to one of major obstacle of electrokinetic cell.
For bringing into play as much as possible the advantage of LiMn2O4 and LiFePO4, and overcome shortcoming separately, by LiMn2O4, LiFePO4 andConductive carbon material three compound use becomes the focus of current research. As LiFePO4/ C and LiMn2O4Mechanical mixture material can makeBattery have good cycle performance and higher specific power (referring to ImachiN, TakanoY, FujimotoH, etal.LayeredCathodeforimprovingsafetyofLi-ionbatteries.JElectrochemS oc, 2007,154 (5): A412-A416; HighRising sun light, Hu Guorong: LiFeP04-LiMn204The impact of blended anode material on battery performance, power technology, 2007,31 (11): 881-884); Chinese patent literature (referring to CN200610032212.3, CN201110131295.2, CN201110395428.7,The Chinese patent literatures such as CN200710077316.0) etc. also have similar report, by conductive carbon material, LiFePO4 and LiMn2O4Form three-phase composite material etc. mechanical mixture, improved the chemical property of material. As can be seen here, by addition compound both physicsThe electric conductivity of carbon has a certain impact to the certain tool of the chemical property of material, this mixing based between different structure positive electrodeUse the main direction that is just becoming the research of current driving force cell positive material and application.
But, make a general survey of the preparation technology of these existing reports, be the direct solid phase mixing of three kinds of components substantially, microstructureUniformity is difficult to control, very limited to improving electric conductivity, stability and the chemical property of material. At present existing Li2CoO2、LiNixCoyMnzO2The report of surface coating LiMn 2 O, it can reduce contacting of electrolyte and spinelle manganic acid lithium material, and it is right to reduceThe corrosion of electrode material, has strengthened cyclical stability, high-temperature storage performance and security (N.V.Kosova, the E.T. of LiMn2O4 Devyatkina,V.V.Kaichev,A.B.Slobodyuk.From‘core–shell’tocompositemixedcathodematerialsforrechargeablelithiumbatteriesbymechanochemicalprocess,SolidStateIonics.2011,192:284 – 288). But these researchs only rest on the surface modification stage at present, do not realize real meaningHeterogeneous nano combined in justice.
As everyone knows, spheroidization can improve tap density and the cyclical stability of positive electrode greatly. Therefore, how by new workSkill, by LiFePO4, LiMn2O4 and conductive carbon realize that three-phase is nano combined simultaneously, nanometer control coated and spheroidization will be to grindStudy carefully personnel's research direction and difficulties.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provides that a kind of spheroidization, nanometer are coated, three-phase is receivedThe three-dimensional complex spherical powder of the multi-level nanostructured mangaic acid lithium/lithium iron phosphate/carbon material that rice structure composite interts, also corresponding providingA kind of processing step is simple, raw material sources are extensive, production cost is low, the aforementioned three-dimensional complex spherical of operating process green non-pollutionThe preparation method of powder body material.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of nanostructured mangaic acid lithium/lithium iron phosphate/carbon three-dimensionalComplex spherical powder material, described three-dimensional complex spherical powder material is mainly by nano-porous structure LiMn2O4, nano-grade lithium iron phosphateWith carbon three phase compositions, and pattern spherical in shape, the particle diameter of described three-dimensional complex spherical powder material is micron order, forms described three-dimensionalThe particle diameter of the primary particle of complex spherical powder material is nanoscale, and described nano-grade lithium iron phosphate and carbon uniform deposition are at nanoporousIn the microsphere surface and/or hole of structure LiMn2O4, nano-porous structure LiMn2O4 in described three-dimensional complex spherical powder material,The mass fraction of nano-grade lithium iron phosphate and carbon is respectively 50%～90%, 5%～45% and 3%～5%.
In the above-mentioned three-dimensional complex spherical powder of nanostructured mangaic acid lithium/lithium iron phosphate/carbon material, preferred, described three-dimensional composite ballsShape powder body material by and only by nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon three phase compositions; Described nano-porous structureLiMn2O4, nano-grade lithium iron phosphate and carbon form the network structure that intert mutually in conjunction with good three-phase at interface.
In the above-mentioned three-dimensional complex spherical powder of nanostructured mangaic acid lithium/lithium iron phosphate/carbon material, preferred, described nanoporous knotThe mass ratio of structure LiMn2O4, nano-grade lithium iron phosphate and carbon is controlled at 5～9: 0.5～4.5: 0.3～0.5.
In the above-mentioned three-dimensional complex spherical powder of nanostructured mangaic acid lithium/lithium iron phosphate/carbon material, preferred, described three-dimensional composite ballsThe particle diameter of shape powder body material is distributed in 5 μ m～30 μ m, and the particle diameter of described primary particle is distributed in 10nm～100nm.
As a total technical conceive, the present invention also provides a kind of above-mentioned nanostructured mangaic acid lithium/lithium iron phosphate/carbon three-dimensional composite ballsThe preparation method of shape powder body material, specifically comprises the following steps:
(1) soluble manganese salting liquid and sodium oxalate solution are added by the mol ratio (mol ratio of solute) of 1: 1～1: 2 simultaneouslyEnter in reactor, fully, after stirring reaction, obtain the spherical manganese oxalate powder of nanostructured;
(2) by the spherical manganese oxalate powder roasting under inert atmosphere obtaining in step (1), sintering temperature be controlled at 300 DEG C～400 DEG C, after roasting, obtain the MnO of porous nanometer structure2Microballoon powder;
(3) carry out inverse by the mass fraction proportioning of described nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon, by inverseThe MnO of rear respective quality2Microballoon powder, lithium salts, molysite, phosphate and carbon source mix, and are placed in reactor, in 170 DEG C～Fully reaction at 200 DEG C of temperature, obtains the three-dimensional complex microsphere powder of LiMn2O4/lithium iron phosphate/carbon semi-finished product;
(4) the three-dimensional complex microsphere powder of the LiMn2O4 obtaining in step (3)/lithium iron phosphate/carbon semi-finished product are mixed to atmosphere at nitrogen hydrogenIn further crystallization processing at 700 DEG C～900 DEG C, obtain the three-dimensional complex spherical of product nanostructured mangaic acid lithium/lithium iron phosphate/carbonPowder body material.
Above-mentioned preparation method, preferred, in described step (1), described soluble manganese salting liquid refer to molar concentration be 0.2M～The manganese sulfate solution of 0.5M or manganese chloride solution; The molar concentration of described sodium oxalate solution is 0.2M～0.5M.
Above-mentioned preparation method, preferred, in described step (1), described reactor is for having churned mechanically flow reactor,The mixing speed of stirring reaction is 500r/min～1000r/min, and the time of stirring reaction is 24h～48h.
Above-mentioned preparation method, preferred, in described step (2), inert atmosphere refer to nitrogen atmosphere, argon gas atmosphere orCarbon dioxide-carbon monoxide mixes atmosphere.
Above-mentioned preparation method, preferred, in described step (3), described reactor is hydrothermal reactor, the reaction time is controlledAt 12h～48h.
Above-mentioned preparation method, preferred, in described step (3), described lithium salts is lithium nitrate, described molysite is ferrous sulfate,Described phosphate is phosphoric acid hydrogen ammonia, and described carbon source refers to phenolic resins, glucose, fructose, lactose, maltose, polyethylene glycolIn at least one.
Above-mentioned preparation method, preferred, in described step (4), the time of crystallization processing is controlled at 2h～4h.
Above-mentioned preparation method, preferred, in described step (4), the mixed atmosphere of nitrogen hydrogen refers to equal-volume H2And N2MixedAtmosphere.
The three-dimensional complex spherical powder of the nanostructured mangaic acid lithium/lithium iron phosphate/carbon material of the invention described above can be used for preparing lithium-ion electricPond positive electrode, its positive electrode of preparing can not only reduce contacting of Mn and electrolyte, and can suppress the dissolving of Mn, carriesThe stability of high cell positive material and electric conductivity, improve its chemical property.
Compared with prior art, the invention has the advantages that:
(1) can to obtain main body be nano-porous structure LiMn2O4 microballoon to technology provided by the invention, its surface and body inner pore phaseMutually deposition one deck LiFePO4 and material with carbon element, forms the nano composite structure that three-phase interts mutually (can referring to Fig. 1), this nanometerThe composite granule particle diameter of composite construction is preferably distributed in 5 μ m～30 μ m, the particle diameter of primary particle be preferably distributed in 10nm～100nm, the multi-level compound and global optimization of, three-phase micro nano structure coated by spheroidization, nanometer, makes of the present inventionThe three-dimensional complex spherical powder of nanostructured mangaic acid lithium/lithium iron phosphate/carbon material list reveals excellent chemical property, at electrode materialApplication in do well.
(2) in the three-dimensional complex spherical powder of nanostructured mangaic acid lithium provided by the invention/lithium iron phosphate/carbon material, due to carrier MnO2The porous of microballoon, nanometer LiFePO4/ C not only can be deposited on the surface of microballoon, and can in hole, deposit,Make LiFePO4 and carbon double-coating in lithium manganate particle surface and duct, intert mutually in conjunction with good three-phase at formation interfaceNetwork structure, this can not only reduce contacting of Mn and electrolyte better, suppresses the dissolving of Mn, and can make LiMn2O4Better protected, the safety and stability of whole complex spherical powder material is better.
(3) in the three-dimensional complex spherical powder of nanostructured mangaic acid lithium provided by the invention/lithium iron phosphate/carbon material, owing to having realizedThe integration of composition of material and material spherical, the tap density that this has just improved composite greatly, also contributes to small product sizeThe raising of specific capacity.
(4) in the three-dimensional complex spherical powder of nanostructured mangaic acid lithium provided by the invention/lithium iron phosphate/carbon material, due at microcosmicIn structure, realized nanometer, micro-nano compound, the carbonaceous conductive network forming in interfacial structure is to mangaic acid reason and LiFePO4 selfElectric conductivity is highly profitable, and comprehensive electrochemical can be further improved.
(5) preparation method of the present invention is simple, raw material sources are extensive, and production cost is low, and production efficiency is high, operating process is greenPollution-free, be easy to industrialization, in commercial Application from now on, there are wide market prospects.
Brief description of the drawings
Fig. 1 is the microstructure schematic diagram of the three-dimensional complex spherical powder of nanostructured mangaic acid lithium of the present invention/lithium iron phosphate/carbon material.
Fig. 2 is the SEM photo of the three-dimensional complex spherical powder material that obtains of the embodiment of the present invention 1.
Fig. 3 is the section S EM figure of the three-dimensional complex spherical powder material that obtains of the embodiment of the present invention 1.
Fig. 4 is that (the present embodiment is mainly table for the section S EM figure of the three-dimensional complex spherical powder material that obtains of the embodiment of the present invention 2Levy the situation that LiFePO4 high-load exists, therefore the constituency of Fig. 4 middle section SEM is the district that LiFePO4 covers LiMn2O4 completelyTerritory).
Fig. 5 is the XRD figure of the three-dimensional complex spherical powder material that obtains of the embodiment of the present invention 2.
Detailed description of the invention
For the ease of understanding the present invention, below in connection with Figure of description and preferred embodiment to the present invention do more comprehensively, carefulGround is described, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, all technical terms of hereinafter using are identical with the implication that those skilled in the art understand conventionally.Technical term used herein, just in order to describe the object of specific embodiment, is not to be intended to limit protection model of the present inventionEnclose.
Apart from special instruction, various reagent, the raw material of using in the present invention is the commodity that can buy from the market or passableThe product making by known method.
Embodiment 1:
The three-dimensional complex spherical powder of one nanostructured mangaic acid lithium of the present invention as shown in Figure 1/lithium iron phosphate/carbon material, its mainly byNano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon three phase compositions, and pattern spherical in shape, this three-dimensional complex spherical powder materialThe particle diameter of material is micron order, and the particle diameter that forms the primary particle of three-dimensional complex spherical powder material is nanoscale, nano-grade lithium iron phosphateIn the microsphere surface and hole of nano-porous structure LiMn2O4, in three-dimensional complex spherical powder material, nanometer is many with carbon uniform depositionThe mass fraction of pore structure LiMn2O4, nano-grade lithium iron phosphate and carbon is respectively 90%, 5% and 5%, i.e. nano-porous structure mangaic acidThe mass ratio of lithium, nano-grade lithium iron phosphate and carbon is controlled at 9: 0.5: 0.5. In the present embodiment three-dimensional complex spherical powder material by andOnly by nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon three phase compositions; And from Fig. 1～Fig. 3, nanoporous knotStructure LiMn2O4, nano-grade lithium iron phosphate and carbon form the network structure that intert mutually in conjunction with good three-phase at interface, and three-dimensional composite ballsThe particle diameter of shape powder body material is distributed in 5 μ m～30 μ m, and the particle diameter of primary particle is distributed in 10nm～100nm.
A preparation method for the three-dimensional complex spherical powder of the nanostructured mangaic acid lithium/lithium iron phosphate/carbon material of above-mentioned the present embodiment, toolBody comprises the following steps:
(1) prepare the manganese sulfate solution of 0.2M and the sodium oxalate solution of 0.4M (sodium oxalate is made precipitating reagent), by 1: 2Manganese sulfate solution and sodium oxalate solution are at room temperature added the flow reactor with mechanical agitation function by solute mol ratio simultaneouslyIn, mixing speed is 500r/min, continuous charging, abundant stirring reaction 48h, the spherical manganese oxalate powder of acquisition nanostructured;
(2) by the spherical manganese oxalate powder roasting under nitrogen atmosphere obtaining in step (1), sintering temperature is controlled at 400 DEG C,After roasting, obtain the MnO of porous nanometer structure2Microballoon powder;
(3) press the quality proportioning 9: 0.5: 0.5 of nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon in the present embodiment productCarry out inverse, by the MnO of respective quality after inverse2Microballoon powder, lithium nitrate, ferrous sulfate, phosphoric acid hydrogen ammonia and glucose are mixedClose evenly, be placed in hydrothermal reactor, at 170 DEG C of temperature, fully react 48h, obtain LiMn2O4/lithium iron phosphate/carbon three-dimensional multipleClose microballoon powder semi-finished product;
(4) the three-dimensional complex microsphere powder of the LiMn2O4 obtaining in step (3)/lithium iron phosphate/carbon semi-finished product are mixed to atmosphere at nitrogen hydrogen(equal-volume H2And N2Mixed atmosphere) at 700 DEG C of temperature further crystallization process 4h, obtain product nano-structure manganeseThe three-dimensional complex spherical powder of acid lithium/lithium iron phosphate/carbon material.
Above-described embodiment obtain three-dimensional complex spherical powder material microcosmic SEM photo as shown in Figure 2, section S EM photo asShown in Fig. 3; Can be found out by Fig. 2 and Fig. 3, in the present embodiment the particle diameter of three-dimensional complex spherical powder material be distributed in 5 μ m～30 μ m, the particle diameter of primary particle is distributed in 10nm～100nm, and can be found out by Fig. 1～Fig. 3, the nanometer phosphorus of the present embodimentAcid iron lithium and carbon uniform deposition in the microsphere surface and hole of nano-porous structure LiMn2O4, and nano-porous structure LiMn2O4,Nano-grade lithium iron phosphate and carbon form the network structure that intert mutually in conjunction with good three-phase at interface.
Theory and practice result all show, the three-dimensional complex spherical powder of nanostructured mangaic acid lithium/lithium iron phosphate/carbon of above-mentioned the present embodimentMaterial can be used for preparing anode material for lithium-ion batteries, and its positive electrode of preparing can not only reduce contacting of Mn and electrolyte, andAnd can suppress the dissolving of Mn, improve stability and the electric conductivity of cell positive material, improve its chemical property.
Embodiment 2:
The three-dimensional complex spherical powder of one nanostructured mangaic acid lithium of the present invention as shown in Figure 1/lithium iron phosphate/carbon material, its mainly byNano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon three phase compositions, and pattern spherical in shape, this three-dimensional complex spherical powder materialThe particle diameter of material is micron order, and the particle diameter that forms the primary particle of three-dimensional complex spherical powder material is nanoscale, nano-grade lithium iron phosphateIn the microsphere surface and hole of nano-porous structure LiMn2O4, in three-dimensional complex spherical powder material, nanometer is many with carbon uniform depositionThe mass fraction of pore structure LiMn2O4, nano-grade lithium iron phosphate and carbon is respectively 50%, 45% and 5%, i.e. nano-porous structure mangaic acidThe mass ratio of lithium, nano-grade lithium iron phosphate and carbon is controlled at 5: 4.5: 0.5. In the present embodiment three-dimensional complex spherical powder material by andOnly by nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon three phase compositions; And from Fig. 1, Fig. 4 and Fig. 5, nanometerLoose structure LiMn2O4, nano-grade lithium iron phosphate and carbon form the network structure that intert mutually in conjunction with good three-phase at interface, and three-dimensionalThe particle diameter of complex spherical powder material is distributed in 5 μ m～30 μ m, and the particle diameter of primary particle is distributed in 10nm～100nm.
A preparation method for the three-dimensional complex spherical powder of the nanostructured mangaic acid lithium/lithium iron phosphate/carbon material of above-mentioned the present embodiment, toolBody comprises the following steps:
(1) prepare the manganese sulfate solution of 0.5M and the sodium oxalate solution of 0.5M (sodium oxalate is made precipitating reagent), by 1: 1Manganese sulfate solution and sodium oxalate solution are at room temperature added the flow reactor with mechanical agitation function by solute mol ratio simultaneouslyIn, mixing speed is 1000r/min, continuous charging, abundant stirring reaction 24h, the spherical manganese oxalate powder of acquisition nanostructured;
(2) by the spherical manganese oxalate powder roasting under Ar atmosphere obtaining in step (1), sintering temperature is controlled at 300 DEG C,After roasting, obtain the MnO of porous nanometer structure2Microballoon powder;
(3) press the quality proportioning 5: 4.5: 0.5 of nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon in the present embodiment productCarry out inverse, by the MnO of respective quality after inverse2Microballoon powder, lithium nitrate, ferrous sulfate, phosphoric acid hydrogen ammonia and phenolic resinsMix, be placed in hydrothermal reactor, at 200 DEG C of temperature, fully react 12h, obtain LiMn2O4/lithium iron phosphate/carbon three-dimensionalComplex microsphere powder semi-finished product;
(4) the three-dimensional complex microsphere powder of the LiMn2O4 obtaining in step (3)/lithium iron phosphate/carbon semi-finished product are mixed to atmosphere at nitrogen hydrogen(equal-volume H2And N2Mixed atmosphere) at 900 DEG C of temperature further crystallization process 2h, obtain product nano-structure manganeseThe three-dimensional complex spherical powder of acid lithium/lithium iron phosphate/carbon material.
As shown in Figure 4, thing phase diffraction divides the microscopic cross SEM photo of the three-dimensional complex spherical powder material that above-described embodiment obtainsAnalyse collection of illustrative plates as shown in Figure 5; Can be found out by Fig. 4 and Fig. 5, in the present embodiment, the particle diameter of three-dimensional complex spherical powder material distributesAt 5 μ m～30 μ m, the particle diameter of primary particle is distributed in 10nm～100nm, and can be found out by Fig. 1, Fig. 4 and Fig. 5, thisThe nano-grade lithium iron phosphate of embodiment and carbon uniform deposition are in the microsphere surface and hole of nano-porous structure LiMn2O4, and nanometer is manyPore structure LiMn2O4, nano-grade lithium iron phosphate and carbon form the network structure that intert mutually in conjunction with good three-phase at interface, and XRD knotFruit show in three-dimensional complex spherical powder material by and only by LiMn2O4、LiFePO4With amorphous C composition.
Theory and practice result all show, the three-dimensional complex spherical powder of nanostructured mangaic acid lithium/lithium iron phosphate/carbon of above-mentioned the present embodimentPositive electrode prepared by material can not only reduce contacting of Mn and electrolyte, and can suppress the dissolving of Mn, improves anodeThe stability of material and electric conductivity, improve its chemical property.
Embodiment 3:
The three-dimensional complex spherical powder of one nanostructured mangaic acid lithium of the present invention as shown in Figure 1/lithium iron phosphate/carbon material, its mainly byNano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon three phase compositions, and pattern spherical in shape, this three-dimensional complex spherical powder materialThe particle diameter of material is micron order, and the particle diameter that forms the primary particle of three-dimensional complex spherical powder material is nanoscale, nano-grade lithium iron phosphateIn the microsphere surface and hole of nano-porous structure LiMn2O4, in three-dimensional complex spherical powder material, nanometer is many with carbon uniform depositionThe mass fraction of pore structure LiMn2O4, nano-grade lithium iron phosphate and carbon is respectively 70%, 27% and 3%, i.e. nano-porous structure mangaic acidThe mass ratio of lithium, nano-grade lithium iron phosphate and carbon is controlled at 7: 2.7: 0.3. In the present embodiment three-dimensional complex spherical powder material by andOnly by nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon three phase compositions; And nano-porous structure mangaic acid as seen from Figure 1,Lithium, nano-grade lithium iron phosphate and carbon form the network structure that intert mutually in conjunction with good three-phase at interface, and three-dimensional complex spherical powderThe particle diameter of material is distributed in 5 μ m～30 μ m, and the particle diameter of primary particle is distributed in 10nm～100nm.
A preparation method for the three-dimensional complex spherical powder of the nanostructured mangaic acid lithium/lithium iron phosphate/carbon material of above-mentioned the present embodiment, toolBody comprises the following steps:
(1) prepare the manganese sulfate solution of 0.4M and the sodium oxalate solution of 0.5M (sodium oxalate is made precipitating reagent), by 1: 1.25Solute mol ratio manganese sulfate solution and sodium oxalate solution are at room temperature added to the flow reactor with mechanical agitation function simultaneouslyIn, mixing speed is 700r/min, continuous charging, abundant stirring reaction 36h, the spherical manganese oxalate powder of acquisition nanostructured;
(2) by the spherical manganese oxalate powder roasting under nitrogen atmosphere obtaining in step (1), sintering temperature is controlled at 350 DEG C,After roasting, obtain the MnO of porous nanometer structure2Microballoon powder;
(3) press the quality proportioning 7: 2.7: 0.3 of nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon in the present embodiment productCarry out inverse, by the MnO of respective quality after inverse2Microballoon powder, lithium nitrate, ferrous sulfate, phosphoric acid hydrogen ammonia and maltose are mixedClose evenly, be placed in hydrothermal reactor, at 180 DEG C of temperature, fully react 24h, obtain LiMn2O4/lithium iron phosphate/carbon three-dimensional multipleClose microballoon powder semi-finished product;
(4) the three-dimensional complex microsphere powder of the LiMn2O4 obtaining in step (3)/lithium iron phosphate/carbon semi-finished product are mixed to atmosphere at nitrogen hydrogen(equal-volume H2And N2Mixed atmosphere) at 800 DEG C of temperature further crystallization process 3h, obtain product nano-structure manganeseThe three-dimensional complex spherical powder of acid lithium/lithium iron phosphate/carbon material.
The particle diameter of the three-dimensional complex spherical powder material that above-described embodiment obtains is distributed in 5 μ m～30 μ m, and the particle diameter of primary particle dividesCloth is at 10nm～100nm, and the nano-grade lithium iron phosphate of the present embodiment and carbon uniform deposition are at the microballoon table of nano-porous structure LiMn2O4In face and hole, and intert mutually in conjunction with good three-phase at nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon formation interfaceNetwork structure, and XRD result show in three-dimensional complex spherical powder material by and only by LiMn2O4、LiFePO4Fixed with nothingShape C composition.
Theory and practice result all show, the three-dimensional complex spherical powder of nanostructured mangaic acid lithium/lithium iron phosphate/carbon of above-mentioned the present embodimentPositive electrode prepared by material can improve stability and the electric conductivity of cell positive material, improves its chemical property.
Embodiment 4:
The three-dimensional complex spherical powder of one nanostructured mangaic acid lithium of the present invention as shown in Figure 1/lithium iron phosphate/carbon material, its mainly byNano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon three phase compositions, and pattern spherical in shape, this three-dimensional complex spherical powder materialThe particle diameter of material is micron order, and the particle diameter that forms the primary particle of three-dimensional complex spherical powder material is nanoscale, nano-grade lithium iron phosphateIn the microsphere surface and hole of nano-porous structure LiMn2O4, in three-dimensional complex spherical powder material, nanometer is many with carbon uniform depositionThe mass fraction of pore structure LiMn2O4, nano-grade lithium iron phosphate and carbon is respectively 70%, 25% and 5%, i.e. nano-porous structure mangaic acidThe mass ratio of lithium, nano-grade lithium iron phosphate and carbon is controlled at 7: 2.5: 0.5. In the present embodiment three-dimensional complex spherical powder material by andOnly by nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon three phase compositions; And nano-porous structure mangaic acid as seen from Figure 1,Lithium, nano-grade lithium iron phosphate and carbon form the network structure that intert mutually in conjunction with good three-phase at interface, and three-dimensional complex spherical powderThe particle diameter of material is distributed in 9 μ m～30 μ m, and the particle diameter of primary particle is distributed in 20nm～100nm.
A preparation method for the three-dimensional complex spherical powder of the nanostructured mangaic acid lithium/lithium iron phosphate/carbon material of above-mentioned the present embodiment, toolBody comprises the following steps:
(1) prepare the manganese sulfate solution of 0.3M and the sodium oxalate solution of 0.45M (sodium oxalate is made precipitating reagent), by 1: 1.5Solute mol ratio manganese sulfate solution and sodium oxalate solution are at room temperature added to the flow reactor with mechanical agitation function simultaneouslyIn, mixing speed is 700r/min, continuous charging, abundant stirring reaction 26h, the spherical manganese oxalate powder of acquisition nanostructured;
(2) by the spherical manganese oxalate powder obtaining in step (1) at CO2Roasting under/CO mixed atmosphere, sintering temperature controlAt 350 DEG C, after roasting, obtain the MnO of porous nanometer structure2Microballoon powder;
(3) press the quality proportioning 7: 2.5: 0.5 of nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon in the present embodiment productCarry out inverse, by the MnO of respective quality after inverse2Microballoon powder, lithium nitrate, ferrous sulfate, phosphoric acid hydrogen ammonia and polyethylene glycol6000 mix, and are placed in hydrothermal reactor, fully react 24h at 200 DEG C of temperature, acquisition LiMn2O4/LiFePO4/The three-dimensional complex microsphere powder of carbon semi-finished product;
(4) the three-dimensional complex microsphere powder of the LiMn2O4 obtaining in step (3)/lithium iron phosphate/carbon semi-finished product are mixed to atmosphere at nitrogen hydrogen(equal-volume H2And N2Mixed atmosphere) at 800 DEG C of temperature further crystallization process 2h, obtain product nano-structure manganeseThe three-dimensional complex spherical powder of acid lithium/lithium iron phosphate/carbon material.
The particle diameter of the three-dimensional complex spherical powder material that above-described embodiment obtains is distributed in 9 μ m～30 μ m, and the particle diameter of primary particle dividesCloth is at 20nm～100nm, and the nano-grade lithium iron phosphate of the present embodiment and carbon uniform deposition are at the microballoon table of nano-porous structure LiMn2O4In face and hole, and intert mutually in conjunction with good three-phase at nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon formation interfaceNetwork structure, and XRD result show in three-dimensional complex spherical powder material by and only by LiMn2O4、LiFePO4Fixed with nothingShape C composition.
Theory and practice result all show, the three-dimensional complex spherical powder of nanostructured mangaic acid lithium/lithium iron phosphate/carbon of above-mentioned the present embodimentPositive electrode prepared by material can improve stability and the electric conductivity of cell positive material, improves its chemical property.
Claims (8)
1. the preparation method of the three-dimensional complex spherical powder of a nanostructured mangaic acid lithium/lithium iron phosphate/carbon material, described three-dimensional complex spherical powder material is mainly by nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon three phase compositions, and pattern spherical in shape, the particle diameter of described three-dimensional complex spherical powder material is micron order, the particle diameter that forms the primary particle of described three-dimensional complex spherical powder material is nanoscale, described nano-grade lithium iron phosphate and carbon uniform deposition are in the microsphere surface and/or hole of nano-porous structure LiMn2O4, nano-porous structure LiMn2O4 in described three-dimensional complex spherical powder material, the mass fraction of nano-grade lithium iron phosphate and carbon is respectively 50%～90%, 5%～45% and 3%～5%, described preparation method specifically comprises the following steps:
(1) soluble manganese salting liquid and sodium oxalate solution are added in reactor by the mol ratio of 1: 1～1: 2 simultaneously, fully, after stirring reaction, obtain the spherical manganese oxalate powder of nanostructured;
(2) by the spherical manganese oxalate powder roasting under inert atmosphere obtaining in step (1), sintering temperature is controlled at 300 DEG C～400 DEG C, obtains the MnO of porous nanometer structure after roasting2Microballoon powder;
(3) carry out inverse by the mass fraction proportioning of described nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon, by the MnO of respective quality after inverse2Microballoon powder, lithium salts, molysite, phosphate and carbon source mix, and are placed in reactor, and fully reaction at 170 DEG C～200 DEG C temperature obtains the three-dimensional complex microsphere powder of LiMn2O4/lithium iron phosphate/carbon semi-finished product;
(4) by the further crystallization processing at 700 DEG C～900 DEG C in the mixed atmosphere of nitrogen hydrogen of the three-dimensional complex microsphere powder of the LiMn2O4 obtaining in step (3)/lithium iron phosphate/carbon semi-finished product, obtain the three-dimensional complex spherical powder of product nanostructured mangaic acid lithium/lithium iron phosphate/carbon material.
2. preparation method according to claim 1, is characterized in that: described three-dimensional complex spherical powder material by and only by nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon three phase compositions; Described nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon form the network structure that intert mutually in conjunction with good three-phase at interface.
3. preparation method according to claim 2, is characterized in that: the mass ratio of described nano-porous structure LiMn2O4, nano-grade lithium iron phosphate and carbon is controlled at 5～9: 0.5～4.5: 0.3～0.5.
4. according to the preparation method described in claim 1,2 or 3, it is characterized in that: the particle diameter of described three-dimensional complex spherical powder material is distributed in 5 μ m～30 μ m, and the particle diameter of described primary particle is distributed in 10nm～100nm.
5. preparation method according to claim 1, is characterized in that, in described step (1), described soluble manganese salting liquid refers to that molar concentration is manganese sulfate solution or the manganese chloride solution of 0.2M～0.5M; The molar concentration of described sodium oxalate solution is 0.2M～0.5M.
6. preparation method according to claim 1, is characterized in that:
In described step (1), described reactor is for having churned mechanically flow reactor, and the mixing speed of stirring reaction is 500r/min～1000r/min, and the time of stirring reaction is 24h～48h;
In described step (3), described reactor is hydrothermal reactor, and the reaction time is controlled at 12h～48h;
In described step (4), the time of crystallization processing is controlled at 2h～4h.
7. according to the preparation method described in claim 1,5 or 6, it is characterized in that, in described step (3), described lithium salts is lithium nitrate, described molysite is ferrous sulfate, described phosphate is phosphoric acid hydrogen ammonia, and described carbon source refers at least one in phenolic resins, glucose, fructose, lactose, maltose, polyethylene glycol.
8. according to the preparation method described in claim 1,5 or 6, it is characterized in that:
In described step (2), inert atmosphere refers to that nitrogen atmosphere, argon gas atmosphere or carbon dioxide-carbon monoxide mix atmosphere;
In described step (4), the mixed atmosphere of nitrogen hydrogen refers to equal-volume H2And N2Mixed atmosphere.
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