CN107215900A - A kind of method in lithium-rich manganese-based anode material oberbau spinel structure - Google Patents

A kind of method in lithium-rich manganese-based anode material oberbau spinel structure Download PDF

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CN107215900A
CN107215900A CN201710473738.3A CN201710473738A CN107215900A CN 107215900 A CN107215900 A CN 107215900A CN 201710473738 A CN201710473738 A CN 201710473738A CN 107215900 A CN107215900 A CN 107215900A
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lithium
based anode
anode material
rich manganese
spinel structure
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苏岳锋
郑玉
陈实
陈来
卢赟
王敬
包丽颖
吴锋
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Beijing Institute of Technology BIT
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Abstract

The present invention relates to a kind of method in lithium-rich manganese-based anode material oberbau spinel structure, belong to field of chemical energy storage battery.Methods described is that lithium-rich manganese-based anode material is added in weakly acidic aqueous solution, carries out Li+With H+Ion exchange, then the positive electrode after ion exchange is carried out into heat treatment makes the deficient lithium structure in top layer be transformed into spinel structure, obtaining top layer has the lithium-rich manganese-based anode material of spinel structure.The method of the invention is that the surface structure of bulk material is transformed into spinel structure, not only ensures the unimpeded of lithium ion transport passage, and improve the high rate performance of lithium-rich manganese-based anode material and improve first all coulombic efficiencies；In addition, methods described can be by adjusting concentration and the processing time of weak acid, the depth of the spinel layer of effective Transfer tectonics, so as to adjust the chemical property of electrode material, this control methods are easy, easy, it is not necessary to it is required that in the strictly control reaction time, repeat reliability high.

Description

A kind of method in lithium-rich manganese-based anode material oberbau spinel structure
Technical field
The present invention relates to a kind of preparation method of lithium-rich manganese-based anode material, more particularly to one kind is in lithium-rich manganese-based anode material Expect the method for oberbau spinel structure, belong to field of chemical energy storage battery.
Background technology
On the one hand, the lithium secondary battery developed rapidly in the urgent need to developing higher capacity of mobile electronic device；The opposing party Face, all previous energy crisis and severe environmental problem force national governments to go into overdrive to promote New-energy electric vehicle industry Development, and the fast-developing of electric automobile will also rely on higher capacity and the faster lithium secondary battery of charge-discharge velocity.To meet This demand, it is necessary first to development high-capacity electrode material of new generation.At present, commercialization anode materials for lithium secondary cells is main Using cobalt acid lithium, LiFePO4 and nickel cobalt manganese (or nickel cobalt aluminium) ternary material, its actual specific capacity is respectively less than 220mAh/g.Cause This, develop the novel anode material of high power capacity has turned into the emphasis that lithium secondary battery is studied.
The xLi that the Thackeray groups of U.S.'s Argonne National Laboratory report for work2MnO3·(1-x)LiMO2(M=Ni, Co, Mn or combinations thereof) Li-like ions cell positive material (referred to as lithium-rich manganese-based anode material), exceeded well over because possessing The specific discharge capacity of Current commercial positive electrode and by extensive concern (M.M.Thackeray, the S.- of the electric industry of lithium H.Kang,C.S.Johnson,J.T.Vaughey,R.Benedek,S.A.Hackney,J.Mater.Chem.2007,17, 3112).Lithium-rich manganese-based anode material after first week activation, specific discharge capacity can exceed that 250mAh/g (Qiu, M.Zhang, L.Wu,J.Wang,Y.Xia,D.Qian,H.Liu,S.Hy,Y.Chen,K.An,Y.Zhu,Z.Liu,Y.S.Meng,Nat Commun 2016,7,12108), and have preferable heat endurance, its initial pyrolyzation temperature is postponed to more than 250 DEG C (H.Deng,I.Belharouak,Y.-K.Sun,K.Amine,J.Mater.Chem.2009,19,4510).However, rich lithium manganese There is also the shortcomings of first all coulombic efficiencies are low, high rate performance is poor for base anode material.Research shows, by lithium-rich manganese-based anode Material surface, which coats embedding oxidate for lithium, can improve first all coulombic efficiencies；It is excellent by constructing hierarchy and exposing { 010 } in order Gesture crystal face can significantly improve high rate performance.
Spinel structure possesses the lithium ion diffusion admittance of three-dimensional, as cladding media packs in lithium-rich manganese-based anode material Surface can effectively improve its high rate performance.However, existing report is had by the surface attachment in electrode material The material of spinel layer structure, this clad is not only difficult to control to its uniformity and thickness, and in charge and discharge cycles process In may come off, fail, in addition.Surface coated complex process, it is difficult to which large-scale application is in production.
The content of the invention
For there is no in the prior art a kind of cheap, efficient and there is spinelle knot with the preparation of bulk material seamless connection The method of the clad of structure, it is an object of the invention to provide one kind in lithium-rich manganese-based anode material oberbau spinel structure Method, this method by the way that the surface structure of bulk material is transformed into spinel structure, not only ensure lithium ion transport passage It is unimpeded, and avoid out-layer Mg-Al spinel structure because structural stress material is come off during charge and discharge cycles, solve The problem of first week coulombic efficiency of lithium-rich manganese-based anode material is low, and improve knot of the electrode material in charge and discharge cycles repeatedly Structure stability.
The purpose of the present invention is achieved through the following technical solutions.
A kind of method in lithium-rich manganese-based anode material oberbau spinel structure, methods described step is as follows：
Lithium-rich manganese-based anode material is added in weakly acidic aqueous solution, stirs to pH rate of change and is less than 0.01min-1When, Separation of solid and liquid is carried out, and isolated solid is washed, dried；Dried solid is placed in more than 250 DEG C again At a temperature of be heat-treated more than 30min, obtaining top layer has the lithium-rich manganese-based anode material of spinel structure.
The chemical formula of the lithium-rich manganese-based anode material is as follows：xLi2MnO3·(1-x)LiMO2, 0 ＜ x ＜ 1, M is Ni, Co One or more of with Mn.
The pH value of the weakly acidic aqueous solution is more than 2 and less than 7.
The preferred carbonic acid of weak acid, acetic acid, propionic acid, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, biphosphate in the weakly acidic aqueous solution Potassium and other dihydric phosphates.
The quality of the ammonium dihydrogen phosphate and the mass ratio of lithium-rich manganese-based anode material are 0.01~50:1, ammonium dihydrogen phosphate Preferred 0.01mol/L~the 1.3mol/L of concentration of the aqueous solution.
Preferably, 2h~10h is heat-treated at 300 DEG C~500 DEG C.
Beneficial effect：
(1) the method for the invention is that the bulk material surface structure of lithium-rich manganese-based anode material is transformed into spinelle knot Structure, that is, the out-layer Mg-Al spinel structure constructed is a part for lithium-rich manganese-based anode material itself, effectively reduces two kinds of differences The interfacial tension of structure, so as to improve structural stability of the electrode material in charge and discharge cycles repeatedly.
(2) spinel structure on the lithium-rich manganese-based anode material surface prepared using the method for the invention has three-dimensional lithium Ion diffusion admittance, passage and the lithium ion diffusion admittance in bulk material script crystal structure on these top layers are connected with each other, It ensure that the unimpeded of in charge and discharge process lithium ion diffusion admittance.This structure significantly improves lithium-rich manganese-based anode material High rate performance, not only makes its under big charging or discharging current (such as 5C, 10C) to have higher specific discharge capacity, and first week activation Speed is remarkably improved, and the specific discharge capacity of its 1C speed activation is suitable with the specific capacity that 0.1C speed is activated, and first All coulombic efficiencies are also raised to more than 88%.
(3) present invention is modified from weakly acidic aqueous solution, and low raw-material cost, Processes and apparatus is simple, it is easy to expand Production；And from acid moderate weak acid such as ammonium dihydrogen phosphate, can avoid damaging the agent structure of electrode material；And pass through The concentration for adjusting weakly acidic aqueous solution simultaneously coordinates adjustment processing time, can the effective spinel layer of Transfer tectonics depth so that The chemical property of electrode material is adjusted, this control methods are easy, easy, it is not necessary to it is required that in the strictly control reaction time, repeat Reliability is high.
(4) present invention original electrodes material used is lithium-rich manganese-based anode material, the out-layer Mg-Al spinel structure transformed Main component is Li-Mn-O, is applied to all modifications containing Mn oxide in this way.
Brief description of the drawings
Fig. 1 is that there is on the top layer after embodiment 1 is modified the lithium-rich manganese-based anode material of spinel structure and comparative example 1 to prepare Original lithium-rich manganese-based anode material X-ray diffraction (XRD) comparison diagram.
Fig. 2 is that the high-resolution that the top layer after embodiment 1 is modified has the lithium-rich manganese-based anode material of spinel structure is transmitted Electron microscope (HRTEM) figure.
Fig. 3 is that the lithium-rich manganese-based anode material that the top layer after being modified using embodiment 1 has spinel structure is assembled Cyclic voltammetric (CV) curve map of CR2025 button cells.
Fig. 4 is the circulation of the CR2025 button cells of the original lithium-rich manganese-based anode material assembling prepared using comparative example 1 Volt-ampere curve figure.
Fig. 5 is that the lithium-rich manganese-based anode material that the top layer after being modified using embodiment 1 has spinel structure is assembled The high rate performance test chart of CR2025 button cells.
Fig. 6 is the multiplying power of the CR2025 button cells of the original lithium-rich manganese-based anode material assembling prepared using comparative example 1 Performance test figure.
Embodiment
To be best understood from the present invention, the present invention is described in further detail with reference to specific embodiment.It should be understood that , embodiment described herein is merely to illustrate and explain the present invention, is not intended to limit the invention.In addition, The end points and any value of disclosed scope are not limited to the accurate scope or value herein, and these scopes or value should be managed Solve as comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, each scope It can be combined with each other between endpoint value and single point value, and individually between point value and obtain one or more new numerical value Scope, these number ranges should be considered as specific open herein.
In following examples：
PH is counted：INSTRUMENT MODEL：Plum Teller-support benefit FE20, China；
High resolution transmission electron microscopy (HRTEM)：INSTRUMENT MODEL：Hitachi H-800, Japan；
X-ray diffractometer：INSTRUMENT MODEL：Rigaku Ultima IV, Japan；
Cyclic voltammetric (CV) is tested：CHI660e electrochemical workstations, China；Test voltage interval is 2V~4.8V, scanning Speed 0.1mV/s；
Inductivity coupled plasma mass spectrometry (ICP) instrument：INSTRUMENT MODEL：Agilent 7500ce, the U.S..
The assembling and test of CR2025 button cells：By positive electrode, acetylene black, PVDF (Kynoar) according to 8:1: 1 mass ratio is made slurry and is coated on aluminium foil, and the aluminium foil of the load slurry of drying is cut into diameter about 1cm with slitter Sequin be used as positive pole, using metal lithium sheet as negative pole, the carbonate solution of Celgard2300 as barrier film, 1M be electrolyte (wherein, solvent is that volume ratio is 1:1 ethylene carbonate and the mixed solution of dimethyl carbonate, solute is LiPF6), in argon gas CR2025 button cells are assembled into glove box；It is electric to the CR2025 buttons assembled using CT2001A Land cell testers Pond carries out constant current charge-discharge test under different current densities, and it is 250mA/g to define 1C current densities, and charging/discharging voltage is interval For 2V~4.6V, test temperature is 30 DEG C；Wherein, the positive electrode is the richness with spinel structure for preparing in embodiment The Nitric Acid Modified prepared in the original lithium-rich manganese-based anode material or comparative example 2 that are prepared in lithium manganese-based anode material, comparative example 1 Lithium-rich manganese-based anode material.
Lithium-rich manganese-based anode material described in embodiment 1~8 and comparative example 2 is original prepared by comparative example 1 Lithium-rich manganese-based anode material.
Embodiment 1
5g lithium-rich manganese-based anode materials are added to 100mL concentration after 0.25mol/L ammonium dihydrogen phosphate aqueous solutions, to carry out Magnetic agitation makes electrode material that Li occur in an acidic solution+—H+Ion exchange, and measure ammonium dihydrogen phosphate aqueous solution with pH meter PH value, until pH value rate of change be less than 0.01min-1When, it is filtered by vacuum, and the solid deionization that suction filtration is obtained Water washing 3 times, then it is placed in 80 DEG C of oven drying 6h；Dried solid is placed in Muffle furnace again, 5h is sintered at 450 DEG C to be made Top layer owes lithium structure and is transformed into spinel structure, furnace cooling, and obtaining top layer has the lithium-rich manganese-based anode material of spinel structure Material.
Fig. 1 has the lithium-rich manganese-based anode material and original lithium-rich manganese-based anode material of spinel structure for the top layer after modification The XRD comparison diagrams of material, it can be seen that the main body that the positive electrode after modification does not change original lithium-rich manganese-based anode material is brilliant Body structure, both typical α-NaFeO2Structure, belongs to R-3m space groups, (006)/(012) and the division of (018)/(110) peak Substantially, Li is presented between θ=20~22 °2MnO3Superlattices peak.But at θ=18~20 ° and θ=44~46 ° two Partial enlarged drawing in understand, (003) peak of the positive electrode after modification and the relatively primitive lithium-rich manganese-based anode material in (104) peak It is micro- to be offset to low angle, illustrate that the interlamellar spacing of the positive electrode after modification increases compared to original lithium-rich manganese-based anode material , this is beneficial to the insertion and abjection of lithium ion.
Fig. 2 is the HRTEM figures of the positive electrode after modification, the top layer original of the positive electrode after modifying as we can see from the figure The arrangement of son and interior atoms shows obvious difference, and interior atoms are arranged in typical layer structure, transition metal layer Atomic Arrangement is continuously close, and has obvious spacing between top layer atom and atom.The top layer atom row of positive electrode after modification Row correspond to a kind of similar LiMn2O4Spinel structure.Just as can be seen that lithium-rich manganese-based anode material top layer from HRTEM figures This spinel structure have more unobstructed Li ion diffusion paths than internal layer structure；Moreover, the spinelle knot on top layer Structure continuously splices with internal layer structure, both ensure that the continuity of lithium ion diffusion, turn avoid between phase and phase Make the problem of structure comes off due to larger lattice strain.
Positive electrode after modification is assembled into CR2025 button cells and carries out electrochemical property test.In order to confirm transformation Surface structure be Spinel, by the battery newly assembled carry out CV tests；In addition, produced to exclude first all electricizing activations The influence of Spinel, CV tests are from open circuit state first to low-voltage scanning direction, and test result is as shown in Figure 3.In Fig. 3 What Segment 1 was represented is the CV curve phases with original lithium-rich manganese-based anode material in Fig. 4 from open circuit state to the negative first paragraph swept Than understanding, the positive electrode after modification has more a small peak at 2.8V or so places, also occurs being located in subsequent CV tests being somebody's turn to do The oxidation peak and reduction peak at place, this feature peak is considered as to be produced by the oxidation or reduction of spinel structure, it was demonstrated that modification Spinel structure can distinguish and that capacity can be contributed is there is in positive electrode afterwards.By CR2025 button cells successively High rate performance test is carried out under 1C, 2C, 5C, 10C, 1C, as a result as shown in Figure 5.It can be seen from high rate performance test result, repair First discharge specific capacity of the positive electrode under 1C after decorations is 259.2mAh/g, and coulombic efficiency discharges for 90.5%, 5C first Specific capacity is 222.3mAh/g, and 10C specific discharge capacities are 201.9mAh/g.
Embodiment 2
5g lithium-rich manganese-based anode materials are added to 100mL concentration after 0.25mol/L ammonium dihydrogen phosphate aqueous solutions, to carry out Magnetic agitation makes electrode material that Li occur in an acidic solution+—H+Ion exchange, and measure ammonium dihydrogen phosphate aqueous solution with pH meter PH value, until pH value rate of change be less than 0.01min-1When, it is filtered by vacuum, and the solid deionization that suction filtration is obtained Water washing 3 times, then it is placed in 80 DEG C of oven drying 6h；Dried solid is placed in Muffle furnace again, 5h is sintered at 300 DEG C to be made Top layer owes lithium structure and is transformed into spinel structure, furnace cooling, and obtaining top layer has the lithium-rich manganese-based anode material of spinel structure Material.
Compared with the XRD spectrum of original lithium-rich manganese-based anode material, the positive electrode after modification does not change original rich lithium The main crystal structure of manganese-based anode material, is also typical α-NaFeO2Structure, belong to R-3m space groups, (006)/(012) and (018)/(110) peak division is obvious, and Li is presented between θ=20~22 °2MnO3Superlattices peak.And θ=18~20 ° with And can see at θ=44~46 °, (003) peak and the relatively primitive lithium-rich manganese-based anode in (104) peak of the positive electrode after modification Material is micro- to be offset to low angle, illustrates that the interlamellar spacing of the positive electrode after modification increases compared to original lithium-rich manganese-based anode material Big, this is beneficial to the insertion and abjection of lithium ion.
It is known that the arrangement of top layer atom and interior atoms of the positive electrode after modification is shown from HRTEM figures Obvious difference, interior atoms are arranged in typical layer structure, and the Atomic Arrangement of transition metal layer is continuously close, and top layer is former There is obvious spacing between son and atom.The surface structure of positive electrode after modification corresponds to a kind of similar LiMn2O4Spinelle Structure, this spinel structure has more unobstructed Li ion diffusion paths than internal layer structure.Moreover, the spinelle on top layer Structure is continuously spliced with internal layer structure, both ensure that the continuity of lithium ion diffusion, turn avoid phase and phase it Between make the problem of structure comes off due to larger lattice strain.
Positive electrode after modification is assembled into CR2025 button cells and carries out electrochemical property test.With original rich lithium manganese The CV curves of base anode material have more one and are located at going back for 2.8V or so compared to understanding in the CV curves of the positive electrode after modification Parent peak, it was demonstrated that there is spinel structure.CR2025 button cells are subjected to high rate performance survey under 1C, 2C, 5C, 10C, 1C successively Examination, it can be seen from test result, first discharge specific capacity of the positive electrode under 1C after modification is 274.8mAh/g, first storehouse Human relations efficiency is that 95.0%, 5C specific discharge capacities are 232.8mAh/g, and 10C specific discharge capacities are 206.9mAh/g.
Embodiment 3
5g lithium-rich manganese-based anode materials are added to 100mL concentration after 0.25mol/L ammonium dihydrogen phosphate aqueous solutions, to carry out Magnetic agitation makes electrode material that Li occur in an acidic solution+—H+Ion exchange, and measure ammonium dihydrogen phosphate aqueous solution with pH meter PH value, until pH value rate of change be less than 0.01min-1When, it is filtered by vacuum, and the solid deionization that suction filtration is obtained Water washing 3 times, then it is placed in 80 DEG C of oven drying 6h；Dried solid is placed in Muffle furnace again, 5h is sintered at 600 DEG C to be made Top layer owes lithium structure and is transformed into spinel structure, furnace cooling, and obtaining top layer has the lithium-rich manganese-based anode material of spinel structure Material.
Compared with the XRD spectrum of original lithium-rich manganese-based anode material, the positive electrode after modification does not change original rich lithium The main crystal structure of manganese-based anode material, is also typical α-NaFeO2Structure, belong to R-3m space groups, (006)/(012) and (018)/(110) peak division is obvious, and Li is presented between θ=20~22 °2MnO3Superlattices peak.And θ=18~20 ° with And can see at θ=44~46 °, (003) peak and the relatively primitive lithium-rich manganese-based anode in (104) peak of the positive electrode after modification Material is micro- to be offset to low angle, illustrates that the interlamellar spacing of the positive electrode after modification increases compared to original lithium-rich manganese-based anode material Big, this is beneficial to the insertion and abjection of lithium ion.
It is known that the arrangement of top layer atom and interior atoms of the positive electrode after modification is shown from HRTEM figures Obvious difference, interior atoms are arranged in typical layer structure, and the Atomic Arrangement of transition metal layer is continuously close, and top layer is former There is obvious spacing between son and atom.The surface structure of positive electrode after modification corresponds to a kind of similar LiMn2O4Spinelle Structure, this spinel structure has more unobstructed Li ion diffusion paths than internal layer structure.Moreover, the spinelle on top layer Structure is continuously spliced with internal layer structure, both ensure that the continuity of lithium ion diffusion, turn avoid phase and phase it Between make the problem of structure comes off due to larger lattice strain.
Positive electrode after modification is assembled into CR2025 button cells and carries out electrochemical property test.With original rich lithium manganese The CV curves of base anode material have more one and are located at going back for 2.8V or so compared to understanding in the CV curves of the positive electrode after modification Parent peak, it was demonstrated that there is spinel structure.CR2025 button cells are subjected to high rate performance survey under 1C, 2C, 5C, 10C, 1C successively Examination, it can be seen from test result, first discharge specific capacity of the positive electrode under 1C after modification is 257.5mAh/g, first storehouse Human relations efficiency is that 93.2%, 5C specific discharge capacities are 218.3mAh/g, and 10C specific discharge capacities are 197.3mAh/g.
Embodiment 4
5g lithium-rich manganese-based anode materials are added to 100mL concentration after 0.25mol/L ammonium dihydrogen phosphate aqueous solutions, to carry out Magnetic agitation makes electrode material that Li occur in an acidic solution+—H+Ion exchange, and measure ammonium dihydrogen phosphate aqueous solution with pH meter PH value, until pH value rate of change be less than 0.01min-1When, it is filtered by vacuum, and the solid deionization that suction filtration is obtained Water washing 3 times, then it is placed in 80 DEG C of oven drying 6h；Dried solid is placed in Muffle furnace again, 2h is sintered at 450 DEG C to be made Top layer owes lithium structure and is transformed into spinel structure, furnace cooling, and obtaining top layer has the lithium-rich manganese-based anode material of spinel structure Material.
Compared with the XRD spectrum of original lithium-rich manganese-based anode material, the positive electrode after modification does not change original rich lithium The main crystal structure of manganese-based anode material, is also typical α-NaFeO2Structure, belong to R-3m space groups, (006)/(012) and (018)/(110) peak division is obvious, and Li is presented between θ=20~22 °2MnO3Superlattices peak.And θ=18~20 ° with And can see at θ=44~46 °, (003) peak and the relatively primitive lithium-rich manganese-based anode in (104) peak of the positive electrode after modification Material is micro- to be offset to low angle, illustrates that the interlamellar spacing of the positive electrode after modification increases compared to original lithium-rich manganese-based anode material Big, this is beneficial to the insertion and abjection of lithium ion.
It is known that the arrangement of top layer atom and interior atoms of the positive electrode after modification is shown from HRTEM figures Obvious difference, interior atoms are arranged in typical layer structure, and the Atomic Arrangement of transition metal layer is continuously close, and top layer is former There is obvious spacing between son and atom.The surface structure of positive electrode after modification corresponds to a kind of similar LiMn2O4Spinelle Structure, this spinel structure has more unobstructed Li ion diffusion paths than internal layer structure.Moreover, the spinelle on top layer Structure is continuously spliced with internal layer structure, both ensure that the continuity of lithium ion diffusion, turn avoid phase and phase it Between make the problem of structure comes off due to larger lattice strain.
Positive electrode after modification is assembled into CR2025 button cells and carries out electrochemical property test.With original rich lithium manganese The CV curves of base anode material have more one and are located at going back for 2.8V or so compared to understanding in the CV curves of the positive electrode after modification Parent peak, it was demonstrated that there is spinel structure.CR2025 button cells are subjected to high rate performance survey under 1C, 2C, 5C, 10C, 1C successively Examination, it can be seen from test result, first discharge specific capacity of the positive electrode under 1C after modification is 270.5mAh/g, first storehouse Human relations efficiency is that 95.19%, 5C specific discharge capacities are 224.1mAh/g, and 10C specific discharge capacities are 205.5mAh/g.
Embodiment 5
5g lithium-rich manganese-based anode materials are added to 100mL concentration after 0.25mol/L ammonium dihydrogen phosphate aqueous solutions, to carry out Magnetic agitation makes electrode material that Li occur in an acidic solution+—H+Ion exchange, and measure ammonium dihydrogen phosphate aqueous solution with pH meter PH value, until pH value rate of change be less than 0.01min-1When, it is filtered by vacuum, and the solid deionization that suction filtration is obtained Water washing 3 times, then it is placed in 80 DEG C of oven drying 6h；Dried solid is placed in Muffle furnace again, 10h is sintered at 450 DEG C Top layer is owed lithium structure and be transformed into spinel structure, furnace cooling, obtaining top layer has the lithium-rich manganese-based anode of spinel structure Material.
Compared with the XRD spectrum of original lithium-rich manganese-based anode material, the positive electrode after modification does not change original rich lithium The main crystal structure of manganese-based anode material, is also typical α-NaFeO2Structure, belong to R-3m space groups, (006)/(012) and (018)/(110) peak division is obvious, and Li is presented between θ=20~22 °2MnO3Superlattices peak.And θ=18~20 ° with And can see at θ=44~46 °, (003) peak and the relatively primitive lithium-rich manganese-based anode in (104) peak of the positive electrode after modification Material is micro- to be offset to low angle, illustrates that the interlamellar spacing of the positive electrode after modification increases compared to original lithium-rich manganese-based anode material Big, this is beneficial to the insertion and abjection of lithium ion.
It can see from HRTEM figures, the arrangement of the top layer atom and interior atoms of the positive electrode after modification is shown Obvious difference, interior atoms are arranged in typical layer structure, and the Atomic Arrangement of transition metal layer is continuously close, and top layer is former There is obvious spacing between son and atom.The surface structure of positive electrode after modification corresponds to a kind of similar LiMn2O4Spinelle Structure, this spinel structure has more unobstructed Li ion diffusion paths than internal layer structure.Moreover, the spinelle on top layer Structure is continuously spliced with internal layer structure, both ensure that the continuity of lithium ion diffusion, turn avoid phase and phase it Between make the problem of structure comes off due to larger lattice strain.
Positive electrode after modification is assembled into CR2025 button cells and carries out electrochemical property test.With original rich lithium manganese The CV curves of base anode material have more one and are located at going back for 2.8V or so compared to understanding in the CV curves of the positive electrode after modification Parent peak, it was demonstrated that there is spinel structure.CR2025 button cells are subjected to high rate performance survey under 1C, 2C, 5C, 10C, 1C successively Examination, it can be seen from test result, first discharge specific capacity of the positive electrode under 1C after modification is 256.1mAh/g, first storehouse Human relations efficiency is that 92.37%, 5C specific discharge capacities are 215.4mAh/g, and 10C specific discharge capacities are 199.9mAh/g.
Embodiment 6
5g lithium-rich manganese-based anode materials are added to 100mL concentration after 0.01mol/L ammonium dihydrogen phosphate aqueous solutions, to carry out Magnetic agitation makes electrode material that Li occur in an acidic solution+—H+Ion exchange, and measure ammonium dihydrogen phosphate aqueous solution with pH meter PH value, until pH value rate of change be less than 0.01min-1When, it is filtered by vacuum, and the solid deionization that suction filtration is obtained Water washing 3 times, then it is placed in 80 DEG C of oven drying 6h；Dried solid is placed in Muffle furnace again, 5h is sintered at 450 DEG C to be made Top layer owes lithium structure and is transformed into spinel structure, furnace cooling, and obtaining top layer has the lithium-rich manganese-based anode material of spinel structure Material.
Compared with the XRD spectrum of original lithium-rich manganese-based anode material, the positive electrode after modification does not change original rich lithium The main crystal structure of manganese-based anode material, is also typical α-NaFeO2Structure, belong to R-3m space groups, (006)/(012) and (018)/(110) peak division is obvious, and Li is presented between θ=20~22 °2MnO3Superlattices peak.And θ=18~20 ° with And can see at θ=44~46 °, (003) peak and the relatively primitive lithium-rich manganese-based anode in (104) peak of the positive electrode after modification Material is micro- to be offset to low angle, illustrates that the interlamellar spacing of the positive electrode after modification increases compared to original lithium-rich manganese-based anode material Big, this is beneficial to the insertion and abjection of lithium ion.
It can see from HRTEM figures, the arrangement of the top layer atom and interior atoms of the positive electrode after modification is shown Obvious difference, interior atoms are arranged in typical layer structure, and the Atomic Arrangement of transition metal layer is continuously close, and top layer is former There is obvious spacing between son and atom.The surface structure of positive electrode after modification corresponds to a kind of similar LiMn2O4Spinelle Structure, this spinel structure has more unobstructed Li ion diffusion paths than internal layer structure.Moreover, the spinelle on top layer Structure is continuously spliced with internal layer structure, both ensure that the continuity of lithium ion diffusion, turn avoid phase and phase it Between make the problem of structure comes off due to larger lattice strain.
Positive electrode after modification is assembled into CR2025 button cells and carries out electrochemical property test.With original rich lithium manganese The CV curves of base anode material have more one and are located at going back for 2.8V or so compared to understanding in the CV curves of the positive electrode after modification Parent peak, it was demonstrated that there is spinel structure.CR2025 button cells are subjected to high rate performance survey under 1C, 2C, 5C, 10C, 1C successively Examination, it can be seen from test result, first discharge specific capacity of the positive electrode under 1C after modification is 268.3mAh/g, first storehouse Human relations efficiency is that 88.2%, 5C specific discharge capacities are 220.2mAh/g, and 10C specific discharge capacities are 192.2mAh/g.
Embodiment 7
5g lithium-rich manganese-based anode materials are added to 100mL concentration after 0.05mol/L ammonium dihydrogen phosphate aqueous solutions, to carry out Magnetic agitation makes electrode material that Li occur in an acidic solution+—H+Ion exchange, and measure ammonium dihydrogen phosphate aqueous solution with pH meter PH value, until pH value rate of change be less than 0.01min-1When, it is filtered by vacuum, and the solid deionization that suction filtration is obtained Water washing 3 times, then it is placed in 80 DEG C of oven drying 6h；Dried solid is placed in Muffle furnace again, 5h is sintered at 450 DEG C to be made Top layer owes lithium structure and is transformed into spinel structure, furnace cooling, and obtaining top layer has the lithium-rich manganese-based anode material of spinel structure Material.
Compared with the XRD spectrum of original lithium-rich manganese-based anode material, the positive electrode after modification does not change original rich lithium The main crystal structure of manganese-based anode material, is also typical α-NaFeO2Structure, belong to R-3m space groups, (006)/(012) and (018)/(110) peak division is obvious, and Li is presented between θ=20~22 °2MnO3Superlattices peak.And θ=18~20 ° with And can see at θ=44~46 °, (003) peak and the relatively primitive lithium-rich manganese-based anode in (104) peak of the positive electrode after modification Material is micro- to be offset to low angle, illustrates that the interlamellar spacing of the positive electrode after modification increases compared to original lithium-rich manganese-based anode material Big, this is beneficial to the insertion and abjection of lithium ion.
It can be seen that repairing from HRTEM figures, the arrangement of the top layer atom and interior atoms of the positive electrode after decorations is shown Obvious difference, interior atoms are arranged in typical layer structure, and the Atomic Arrangement of transition metal layer is continuously close, and top layer is former There is obvious spacing between son and atom.The surface structure of positive electrode after modification corresponds to a kind of similar LiMn2O4Spinelle Structure, this spinel structure has more unobstructed Li ion diffusion paths than internal layer structure.Moreover, out-layer Mg-Al spinel knot Structure continuously splices with internal layer structure, both ensure that the continuity of lithium ion diffusion, turn avoid between phase and phase Make the problem of structure comes off due to larger lattice strain.
Positive electrode after modification is assembled into CR2025 button cells and carries out electrochemical property test.With original rich lithium manganese The CV curves of base anode material have more one and are located at going back for 2.8V or so compared to understanding in the CV curves of the positive electrode after modification Parent peak, it was demonstrated that there is spinel structure.CR2025 button cells are subjected to high rate performance survey under 1C, 2C, 5C, 10C, 1C successively Examination, it can be seen from test result, first discharge specific capacity of the positive electrode under 1C after modification is 257.5mAh/g, first storehouse Human relations efficiency is that 89.8%, 5C specific discharge capacities are 222.3mAh/g, and 10C specific discharge capacities are 193.1mAh/g.
Embodiment 8
5g lithium-rich manganese-based anode materials are added to 100mL concentration after 1.25mol/L ammonium dihydrogen phosphate aqueous solutions, to carry out Magnetic agitation makes electrode material that Li occur in an acidic solution+—H+Ion exchange, and measure ammonium dihydrogen phosphate aqueous solution with pH meter PH value, until pH value rate of change be less than 0.01min-1When, it is filtered by vacuum, and the solid deionization that suction filtration is obtained Water washing 3 times, then it is placed in 80 DEG C of oven drying 6h；Dried solid is placed in Muffle furnace again, 5h is sintered at 450 DEG C to be made Top layer owes lithium structure and is transformed into spinel structure, furnace cooling, and obtaining top layer has the lithium-rich manganese-based anode material of spinel structure Material.
Compared with the XRD spectrum of original lithium-rich manganese-based anode material, the positive electrode after modification does not change original rich lithium The main crystal structure of manganese-based anode material, is also typical α-NaFeO2Structure, belong to R-3m space groups, (006)/(012) and (018)/(110) peak division is obvious, and Li is presented between θ=20~22 °2MnO3Superlattices peak.And θ=18~20 ° with And can see at θ=44~46 °, (003) peak and the relatively primitive lithium-rich manganese-based anode in (104) peak of the positive electrode after modification Material is micro- to be offset to low angle, illustrates that the interlamellar spacing of the positive electrode after modification increases compared to original lithium-rich manganese-based anode material Big, this is beneficial to the insertion and abjection of lithium ion.
It can see from HRTEM figures, the arrangement of the top layer atom and interior atoms of the positive electrode after modification is shown Obvious difference, interior atoms are arranged in typical layer structure, and the Atomic Arrangement of transition metal layer is continuously close, and top layer is former There is obvious spacing between son and atom.The surface structure of positive electrode after modification corresponds to a kind of similar LiMn2O4Spinelle Structure, this spinel structure has more unobstructed Li ion diffusion paths than internal layer structure.Moreover, out-layer Mg-Al spinel knot Structure continuously splices with internal layer structure, and this both ensure that the continuity of lithium ion diffusion, turn avoid phase and phase it Between make the problem of structure comes off due to larger lattice strain.
Positive electrode after modification is assembled into CR2025 button cells and carries out electrochemical property test.With original rich lithium manganese The CV curves of base anode material have more one and are located at going back for 2.8V or so compared to understanding in the CV curves of the positive electrode after modification Parent peak, it was demonstrated that there is spinel structure.CR2025 button cells are subjected to high rate performance survey under 1C, 2C, 5C, 10C, 1C successively Examination, it can be seen from test result, first discharge specific capacity of the positive electrode under 1C after modification is 266.4mAh/g, first storehouse Human relations efficiency is that 93.9%, 5C specific discharge capacities are 223.4mAh/g, and 10C specific discharge capacities are 207mAh/g.
The lithium-rich manganese-based anode material for having spinel structure by the top layer after to being modified in embodiment 1,6,7,8 is carried out ICP tests understand that top layer has Li amounts contained in the lithium-rich manganese-based anode material of spinel structure with biphosphate ammonium concentration Increase and reduce, illustrate ion exchange degree with biphosphate ammonium concentration increase and deepen.
Comparative example 1
Original lithium-rich manganese-based anode material is synthesized with carbonate co-precipitation, and specific method is as follows：According to Mn:Ni:Co= 4:1:Manganese sulfate, nickel sulfate and cobaltous sulfate are dissolved in deionized water by 1 mol ratio, obtain 2mol/L sulfate solution； Configure the alkaline aqueous solution containing 2mol/L sodium carbonate and 0.02mol/L ammoniacal liquor；And the molal quantity and sulfate of sodium carbonate Total mole number ratio is 1.05:1；Above-mentioned sulfate solution and alkaline aqueous solution are added continuously to carry respectively with peristaltic pump to stir In the reactor for mixing device and logical nitrogen, and by adjusting the addition speed control pH value of sulfate solution or alkaline aqueous solution, Under nitrogen protection atmosphere, controlling reaction temperature is 55 DEG C, and pH is stabilized to after 8, reaction 6h, by obtained precipitation presoma repeatedly Washing and filtering, then be placed at 80 DEG C and be dried in vacuo 12h；By dried precipitation presoma and Li2CO3According to rubbing for Li/Mn=2 You are than ground and mixed, by the first pre-burning 5h at 500 DEG C of well mixed powder, then are warming up to 900 DEG C of calcining 12h, furnace cooling, Obtain stratiform lithium-rich manganese-based anode material.
It was found from the XRD spectra in Fig. 2, prepared original lithium-rich manganese-based anode material is typical α-NaFeO2Knot Structure, belongs to R-3m space groups, and (006)/(012) and the division of (018)/(110) peak are obvious, and Li is presented between θ=20~22 °2MnO3 Superlattices peak.
Original lithium-rich manganese-based anode material prepared by this comparative example is assembled into CR2025 button cells.CV test results As shown in figure 4, in the scanning of first paragraph, not occurring obvious reduction peak；In two sections of subsequent tests, at 4V and 4.5V There are two obvious oxidation peaks, Ni is correspond to respectively2+/Co3+Oxidation and Li2MnO3Activation, the original lithium-rich manganese-based anode The reduction peak of material is in more than 2.8V, in 2.8V or so without recognizable reduction peak.Successively under 1C, 2C, 5C, 10C, 1C High rate performance test is carried out, test result is as shown in Figure 6.It can be seen from test result, the original rich lithium prepared by this comparative example First discharge specific capacity of the manganese-based anode material under 1C is 233.2mAh/g, and coulombic efficiency is 82.4%, 5C electric discharge ratios first Capacity is 180.8mAh/g, and 10C specific discharge capacities are 153.4mAh/g.
Comparative example 2
0.5g lithium-rich manganese-based anode materials are added to 100mL concentration after 0.05mol/L aqueous solution of nitric acid, to carry out magnetic force Stirring makes electrode material that Li occur in an acidic solution+—H+Ion exchange, and with pH meter measure aqueous solution of nitric acid pH value, directly Rate of change to pH value is less than 0.01min-1When, it is filtered by vacuum, and the solid that suction filtration is obtained is washed with deionized 3 It is secondary, then it is placed in 80 DEG C of oven drying 6h；Dried solid is placed in Muffle furnace again, 5h is sintered at 450 DEG C, it is cold with stove But, the lithium-rich manganese-based anode material of Nitric Acid Modified is obtained.
The lithium-rich manganese-based anode material of prepared Nitric Acid Modified is assembled into CR2025 button cells, successively 1C, 2C, High rate performance test is carried out under 5C, 10C, 1C, it can be seen from test result, the positive electrode prepared by this comparative example is under 1C First discharge specific capacity is 217.2mAh/g, and coulombic efficiency is that 88.1%, 5C specific discharge capacities are 172.6mAh/g, 10C first Specific discharge capacity is 141.2mAh/g.
By above-described embodiment and the test result of comparative example, the present invention provide in lithium-rich manganese-based anode material The method of oberbau spinel structure, not only effect is distinguished, can significantly improve the high rate performance of electrode material and first week Coulombic efficiency, and low cost of raw materials, asepsis environment-protecting, whole technological process is simple, efficient, environmental protection, and experiment condition is wide General, reliability is high, with good prospects for commercial application.

Claims (5)

1. a kind of method in lithium-rich manganese-based anode material oberbau spinel structure, it is characterised in that：Methods described step It is as follows：
Lithium-rich manganese-based anode material is added in weakly acidic aqueous solution, stirs to pH rate of change and is less than 0.01min-1When, carry out Separation of solid and liquid, and isolated solid washed, is dried；Dried solid is placed in more than 250 DEG C of temperature again Lower heat treatment more than 30min, obtaining top layer has the lithium-rich manganese-based anode material of spinel structure；
The chemical formula of the lithium-rich manganese-based anode material is as follows：xLi2MnO3·(1-x)LiMO2, 0 ＜ x ＜ 1, M is Ni, Co and Mn One or more of；The pH value of the weakly acidic aqueous solution is more than 2 and less than 7.
2. a kind of method in lithium-rich manganese-based anode material oberbau spinel structure according to claim 1, it is special Levy and be：Weak acid in the weakly acidic aqueous solution is carbonic acid, acetic acid, propionic acid, ammonium dihydrogen phosphate, sodium dihydrogen phosphate or biphosphate Potassium.
3. a kind of method in lithium-rich manganese-based anode material oberbau spinel structure according to claim 2, it is special Levy and be：The quality of the ammonium dihydrogen phosphate and the mass ratio of lithium-rich manganese-based anode material are 0.01~50:1.
4. a kind of method in lithium-rich manganese-based anode material oberbau spinel structure according to claim 2, it is special Levy and be：The concentration of ammonium dihydrogen phosphate aqueous solution is 0.01mol/L~1.3mol/L.
5. a kind of method in lithium-rich manganese-based anode material oberbau spinel structure according to claim 1, it is special Levy and be：Dried solid is placed in heat treatment 2h~10h at 300 DEG C~500 DEG C.
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CN111710866A (en) * 2020-06-29 2020-09-25 昆山宝创新能源科技有限公司 Core-shell structure lithium-rich manganese-based composite cathode material and preparation method and application thereof
CN112038615A (en) * 2020-10-13 2020-12-04 昆山宝创新能源科技有限公司 Lithium-rich manganese-based composite cathode material and preparation method and application thereof
CN112290009A (en) * 2020-10-30 2021-01-29 清华大学深圳国际研究生院 Manganese-based lithium-rich oxide cathode material, preparation method thereof and electrochemical device using manganese-based lithium-rich oxide cathode material
CN114665070A (en) * 2020-12-22 2022-06-24 北京卫蓝新能源科技有限公司 Lithium-rich manganese-based composite cathode material and preparation method and application thereof
CN113247966A (en) * 2020-12-31 2021-08-13 宁波容百新能源科技股份有限公司 Lithium-rich manganese-based precursor, positive electrode material and preparation method thereof
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CN114497533A (en) * 2022-01-27 2022-05-13 西南石油大学 In-situ spinel modified low-cobalt spherical lithium-rich manganese-based positive electrode material and preparation method thereof
CN114639821A (en) * 2022-03-20 2022-06-17 北京工业大学 Surface modification method of monocrystal-like gradient lithium-rich manganese-based layered oxide
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CN115692682A (en) * 2022-12-16 2023-02-03 中南大学 Modified lithium-rich manganese-based positive electrode material with stable structure, preparation method of modified lithium-rich manganese-based positive electrode material and lithium ion battery

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