CN116190593A - Lithium battery positive electrode material with mixed phase structure, and preparation method and application thereof - Google Patents

Lithium battery positive electrode material with mixed phase structure, and preparation method and application thereof Download PDF

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CN116190593A
CN116190593A CN202211616898.6A CN202211616898A CN116190593A CN 116190593 A CN116190593 A CN 116190593A CN 202211616898 A CN202211616898 A CN 202211616898A CN 116190593 A CN116190593 A CN 116190593A
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lithium
lamellar
positive electrode
lithium battery
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潘锋
赵庆贺
林海
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Unnamed Battery Technology Shenzhen Co ltd
Peking University Shenzhen Graduate School
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Unnamed Battery Technology Shenzhen Co ltd
Peking University Shenzhen Graduate School
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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Abstract

The application discloses a lithium battery anode material with a mixed phase structure, and a preparation method and application thereof. The lithium battery positive electrode material has a mixed phase structure of lamellar phase and non-lamellar phase in a crystal structure, and the lamellar phase and the non-lamellar phase are alternately arranged. In the lithium battery anode material, in the high-voltage charging process, lattice oxygen migration and oxygen precipitation processes in the lamellar phase are inhibited by adjacent non-lamellar phases, so that irreversible oxygen loss and structural disturbance of the lamellar phase in the circulation process are relieved, the structural stability of the lamellar phase is improved, and voltage attenuation is inhibited; as same asAnd when the cathode material is in a charge-discharge state, the lattice parameter change of the cathode material is reduced due to the synergistic effect of the lamellar phase and the non-lamellar phase, and the generation of microcracks in particles is reduced. Therefore, the lithium battery positive electrode material of the application shows the energy of more than 440mAh g at the high voltage of more than 4.5V ‑1 And exhibits excellent electrochemical properties, and excellent reversible capacity, rate and cycle stability.

Description

Lithium battery positive electrode material with mixed phase structure, and preparation method and application thereof
Technical Field
The application relates to the technical field of lithium battery anode materials, in particular to a lithium battery anode material with a mixed phase structure, and a preparation method and application thereof.
Background
The permeability of the global new energy automobile market is rapidly improved, the power battery is in vigorous demand, and the research and development and industrialization development of the lithium battery anode material are greatly promoted. The layered anode material is a main stream anode material of the current lithium battery anode material, and comprises lithium cobaltate, nickel cobalt Meng Sanyuan material, lithium-rich manganese anode material and the like, but the layered materials can generate oxidation-reduction process of lattice oxygen under high-voltage service conditions (voltage is more than 4.5V), which leads to severe phase structure evolution, reduced circulation capacity and voltage attenuation. Taking lithium-rich manganese-based positive electrode material as an example, the positive electrode material is a typical positive electrode material of a lithium ion battery, can generate reversible oxidation-reduction reaction of anions and cations, and has discharge specific capacity far higher than that of a high-voltage lithium cobalt oxide and high-nickel ternary positive electrode material. The lithium-rich manganese-based positive electrode material has the advantages of high specific capacity and strong endurance, and is a next-generation new energy automobile lithium ion battery positive electrode material with great development potential. The lithium-rich manganese-based positive electrode material has great application potential in developing high-energy-density lithium batteries, in particular to all-solid-state lithium metal batteries. In the near future, along with the reduction of lithium salt price, the lithium-rich manganese-based positive electrode material is expected to be applied to the market. Studies have shown that lithium-rich manganese-based cathode materials have demonstrated potential market space in the order of more than one trillion.
In 1997, numata et al reported layered Li for the first time 2 MnO 3 ·LiCoO 2 Solid solution material, nearly 280mAh g was obtained -1 The initial discharge capacity of the lithium-rich manganese material is started. Lithium-rich manganese-based positive electrode material xLiMO 2 ·(1-x)Li 2 MnO 3 Wherein M is a doping element, which is a material of great interest in recent years and industry, and has a theoretical capacity of more than 300mAh g -1 The actual capacity exceeds 200mAh g -1 The working voltage is about 4.5V, and the energy density is high; therefore, the material has the potential of being developed into a positive electrode material of a power battery. Currently, both the academia and the industry are concerned with the development and application of pure Mn-based or low-doped lithium-rich manganese anodes.
In general, the lithium-rich manganese positive electrode material has a solid solution structure of lithium-rich lithium manganate and classical layered lithium transition metal oxide, and is a two-phase compound uniformly mixed on a nanometer scale. It is generally believed that one of the two phase structures in pure manganese-based lithium-rich manganese positive electrode materials is layered Li 2 MnO 3 Belonging to the c2/m space group, monoclinic system, wherein the 3a site is replaced by Li + Occupied 3b site is occupied by 1/3 of Li + And Mn of 2/3 4+ Occupied, 6c site by O 2- Ion occupation; the other is LiMnO 2 The layered structure belongs to the R-3m space group, the hexagonal system, wherein the 3a site is replaced by Li + Occupied 3b site by Mn 3+ Occupied, 6c site by O 2- And (3) occupying ions. Thus, the molecular formula of pure manganese-based lithium-rich manganese material can be written as xLiMnO 2 ·(1-x)Li 2 MnO 3 Wherein x is more than or equal to 0 and less than or equal to 1.
The high capacity and high voltage characteristics of the lithium-rich manganese anode material have different degrees of correlation with the composition, structure, size and morphology of the lithium-rich manganese anode material. The conventional research suggests that the capacity and voltage change mechanism of lithium-rich manganese is "multi-atom participation and a complex process with sequential tendency", which is the cause of the failure to stably maintain the ultrahigh capacity and voltage for many times. Among them, oxygen valence, oxygen migration and even oxygen precipitation in the lattice frame at high voltage are one of the root causes of capacity fade and voltage fade.
Although lithium-rich manganese positive electrode materials exhibit the great advantages of high capacity, high voltage, and low cost; however, the disadvantages of poor conductivity, low capacity utilization and poor cycle stability also restrict the industrial application of the materials. Therefore, how to inhibit the oxygen valence and oxygen migration process and enhance the reversible capacity, multiplying power and cycling stability of the lithium-manganese-rich positive electrode material from the standpoint of crystal structure design is a research focus and difficulty of all layered structure materials including the lithium-manganese-rich positive electrode material.
Disclosure of Invention
The application aims to provide a novel lithium battery anode material with a mixed phase structure, and a preparation method and application thereof.
The application adopts the following technical scheme:
in one aspect, the application discloses a lithium battery positive electrode material with a mixed phase structure, wherein the crystal structure of the lithium battery positive electrode material is provided with a mixed phase structure of lamellar phases and non-lamellar phases, and the lamellar phases and the non-lamellar phases are arranged in a spaced manner.
The lithium battery anode material has the crystal with the mixed phase structure that lamellar phases and non-lamellar phases are alternately arranged, and the lattice oxygen migration and oxygen precipitation processes in the lamellar phase structure are inhibited by the adjacent non-lamellar phases in the high-voltage charging process, so that irreversible oxygen loss and structural disturbance of the lamellar phases in the circulation process are greatly relieved, the stability of the lamellar phase structure is improved, and voltage attenuation is inhibited; meanwhile, the synergistic effect of the lamellar phase and the non-lamellar phase also reduces the change of lattice parameters of the lithium battery anode material in the charge and discharge process, and reduces the generation of microcracks in particles. Therefore, the lithium battery positive electrode material of the application shows the energy of more than 440mAh g at the high voltage of more than 4.5V -1 And has excellent reversible capacity, excellent multiplying power and cycling stability, and excellent electrochemical performance under high-voltage charge and discharge conditions.
In the crystal structure of the positive electrode material of the lithium battery, lamellar phases and non-lamellar phases are alternately arranged to form a microstructure similar to mosaic distribution. For example, the lamellar phase and the non-lamellar phase are arranged from any direction, and lamellar phase-non-lamellar phase-non-lamellar phase are arranged so as to be spaced from each other.
In one implementation of the present application, the non-lamellar phase is on the nanoscale. Preferably, the nanoscale is from 0.5 to 10nm, i.e. the non-lamellar phase is from 0.5 to 10nm.
It should be noted that the main effect of the non-lamellar phase in the present application is to improve structural stability by inhibiting lattice oxygen migration and oxygen precipitation processes in the adjacent lamellar phase structure, and to improve rate performance as a conventional channel for high-speed ions and/or electrons. The scale of the non-lamellar phase of the present application is preferably 0.5-10nm, such as below 0.5nm, then the phase is generally regarded as crystal defects rather than a separate non-lamellar phase structure; if the non-lamellar phase is more than 10nm, the proportion of the non-lamellar phase in the entire positive electrode material increases, and the increase in the proportion is detrimental to the positive electrode material capacity since the non-lamellar phase is not a major capacity-contributing phase. Therefore, to ensure the comprehensive performance of the positive electrode material, the scale of the non-lamellar phase is preferably controlled between 0.5 and 10nm through process control in the synthesis process.
In one implementation of the present application, the mixed phase structure of the lamellar phase and the non-lamellar phase is uniformly distributed in the particles of the positive electrode material of the lithium battery.
It should be noted that, in the lithium battery positive electrode material of the present application, one of the effects of the non-lamellar phase is to reduce the overall crystal structure parameter variation of the positive electrode material and reduce the generation of internal microcracks by the synergistic effect with the lamellar phase. The mixed phase positive electrode material has a layered phase structure, wherein the slippage of a TM-O layer (TM comprises Ni, co, mn and the like) is a main reason for the variation of lattice parameters of the positive electrode material during charge and discharge. The non-lamellar nano phase with the dimension of 0.5-10nm is uniformly distributed in the crystal structure of the material, so that the slippage of a TM-O layer in the lamellar phase structure can be effectively inhibited. In the traditional positive electrode material protection strategy, the non-lamellar phase is only concentrated on the surface of the positive electrode material, and although the interfacial side reaction of the material under the high-voltage service condition can be inhibited, the problem of microcrack generation caused by the change of lattice parameters in the charge and discharge process is not improved. Therefore, in the application, the mixed phase structure of the lamellar phase and the non-lamellar phase is uniformly distributed in the positive electrode material particles, so that the problem of internal microcrack generation caused by lattice parameter change can be effectively relieved.
In one implementation of the present application, interphase interfacial domain lattice adaptation of lamellar and non-lamellar phases.
It should be noted that, the lattice domain lattice adaptation between the mixed phase structures of the positive electrode material can effectively relieve the lattice disorder of the two-phase interface structure and the lattice internal stress condition caused by the phase structure difference. Meanwhile, the lattice adaptation of the two-phase interphase interface crystal domains is also beneficial to the efficient transmission of lithium ions in the positive electrode material crystal structure frame, and the rate capability of the material is improved.
In one implementation of the present application, the non-lamellar phase includes at least one of a spinel phase, a perovskite phase, and a rock salt phase.
It should be noted that, the non-lamellar phase in the positive electrode material of the application, whether it is a spinel phase, a perovskite phase or a rock salt phase structure, can realize two-phase lattice adaptation with the lamellar phase, which ensures lower lattice disorder and internal stress inside the crystal structure of the material; meanwhile, the three phase structures all contain a lithium ion three-dimensional transmission network, so that efficient lithium ion transmission can be realized; and, all of the three phase structures exhibit higher structural stability than the lamellar phase, which is a structural origin that effectively inhibits oxygen migration and oxygen precipitation.
In one implementation of the present application, the non-lamellar phase has a relatively high ionic and/or electronic conductivity to ensure efficient lithium ion and electron transport. Typically, the lithium ion conductivity and the electron conductivity in the non-lamellar phase structure are both greater than 10 -5 S cm -1 。
In one implementation of the present application, the non-lamellar phase improves structural stability of the lamellar phase by inhibiting lattice oxygen migration and/or oxygen evolution processes, thereby improving the cycling stability of the lithium battery anode material at high voltages. High voltage in this application refers to voltages greater than 4.4V or greater than 4.5V.
In one implementation of the present application, the molecular formula of the battery positive electrode active material is Li x TM y O 2 A z Wherein x is more than or equal to 1 and less than or equal to 2, y is more than or equal to 0.5 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.2, and TM is at least one of Mn, co, ni, al, ti, zr and Nb; a is F, BO 3 、SiO 4 、PO 4 And SO 4 At least one of them.
In one implementation of the present application, the lamellar phase has the formula Li 2 TMO 3 Or LiTMO 2 Wherein, TM is at least one of Mn, co and Ni.
In one implementation of the present application, lithium and TM inversion are present in the lamellar phase.
In one implementation of the present application, the content of lithium and TM inversion is 1-40%.
In the present application, the case where lithium and TM in the lamellar phase are reversed refers to a phenomenon in which a part of TM ions in the transition metal layer are position-exchanged with lithium ions in the lithium layer. Through the inversion of lithium and TM, the crystal structure parameters of the mixed phase structure are regulated and optimized, so that the lattice adaptation between lamellar and non-lamellar phases is better realized, the lattice stress of a two-phase interface is reduced, and the high cyclic stability and capacity of the positive electrode material of the mixed phase structure are played a key role. The ease of matching between the two phases varies for different combinations of lamellar and non-lamellar phases, which results in different amounts of lithium and TM inversion in the lamellar phase. In the application, at least 1% of lithium and TM inversion sites exist in the lamellar phase due to the difference of two-phase structures; meanwhile, in order to secure the basic structural framework of the lamellar phase, at most 40% of TM in the transition metal layer enters the lithium layer.
In one implementation of the present application, the molecular formula of the non-lamellar phase is spinel phase Li x TM 2 O 4 Perovskite phase LiTMO 3 Or rock salt phase Li x TM 1-x O, wherein x is more than or equal to 0 and less than or equal to 1, and TM is at least one of Mn, co, ni, al, ti, zr and Nb.
In one implementation of the present application, lithium and TM miscibility is present in the non-lamellar phase.
In one implementation of the present application, the lithium and TM mixed content is 1% -10%.
In the present application, the presence of lithium and TM in the non-lamellar phase means a phenomenon in which Li and TM occupy a certain proportion of the cationic sites in the crystal structure together. Through lithium and TM mixed arrangement, the crystal structure parameters of the non-lamellar phase are optimized to better match the crystal structure of the lamellar phase, and the conditions of lattice stress and lattice disturbance of a two-phase interface are reduced, so that the lithium and TM mixed arrangement plays a key role in high cycle stability and capacity of the positive electrode material with the mixed phase structure. In this application, the mixed phase structure characteristic of the positive electrode material necessarily results in more than 1% of lithium and TM mixed row being present in the non-lamellar phase, but the proportion of lithium and TM mixed row present in the crystal structure is less, typically not more than 10% due to the higher stability of the lamellar phase crystal structure compared to the non-lamellar phase.
In one implementation of the present application, the lithium battery positive electrode material is large primary particles, or secondary particles formed by stacking small primary particles; wherein the size of the large primary particles is 1-20 μm; the size of the secondary particles is 1-20 mu m; the size of the small primary particles is 50 nm-2. Mu.m.
The positive electrode material of the lithium battery can be primary particles or secondary particles formed by stacking the primary particles, and the positive electrode material is specifically determined according to requirements.
In one implementation of the present application, the interphase interfacial domain size of the lamellar phase and the non-lamellar phase is from 0.5 to 10nm.
The other side of the application discloses a preparation method of the lithium battery anode material, which comprises the step of obtaining the lithium battery anode material with a mixed phase structure in which lamellar phases and non-lamellar phases are alternately arranged in a crystal structure by adopting at least one of a high-temperature sintering method, a chemical method and an electrochemical method.
In one implementation mode of the application, the chemical method comprises the steps of placing the sintered and synthesized lithium-rich manganese-based positive electrode material into molten salt containing at least one of lithium nitrate, lithium chloride and lithium oxide, and treating for 1-24 hours at the temperature of 250-350 ℃ to obtain the lithium battery positive electrode material with a layered phase and non-layered phase mixed phase structure.
In one implementation mode of the application, the electrochemical method comprises the steps of mixing sintered and synthesized lithium-rich manganese-based positive electrode material, conductive carbon and polyvinylidene fluoride binder in a ratio of 90:5:5 to prepare a pole piece, and placing the pole piece in lithium salt-containing electrolyte for charging and discharging for not more than 3 circles to obtain the lithium battery positive electrode material with a layered phase and non-layered phase mixed phase structure.
In one implementation mode of the application, a high-temperature sintering method is preferably adopted, and comprises the steps of mixing and sintering multiphase mixed precursors for preparing the lithium battery anode material with lithium carbonate according to a proportion, wherein the sintering temperature is 800-1000 ℃, and the sintering time is 1-24 hours, so as to obtain the lithium battery anode material with a lamellar phase and non-lamellar phase mixed phase structure; the multiphase mixed precursor is oxide of each metal element in the positive electrode material of the lithium battery.
The application discloses application of the lithium battery anode material in preparation of a power battery, an energy storage battery or a lithium ion battery of a 3C consumer electronic product, an unmanned aerial vehicle or an electronic cigarette.
Still another aspect of the present application discloses a lithium ion battery employing the lithium battery anode material of the present application.
The beneficial effects of this application lie in:
in the lithium battery anode material, in the high-voltage charging process, lattice oxygen migration and oxygen precipitation process in a lamellar phase structure are inhibited by adjacent non-lamellar phases, so that irreversible oxygen loss and structural disturbance of the lamellar phase in the circulation process are relieved, the stability of the lamellar phase structure is improved, and voltage attenuation is inhibited; meanwhile, the synergistic effect of the lamellar phase and non-lamellar phase mixed phase structure also reduces the change of lattice parameters of the positive electrode material in the charge and discharge process, and reduces the generation of microcracks in particles. Therefore, the lithium battery positive electrode material of the application shows the energy of more than 440mAh g at the high voltage of more than 4.5V -1 And exhibits excellent electrochemical properties, and excellent reversible capacity, rate and cycle stability.
Drawings
Fig. 1 is a schematic diagram of mosaic mixing distribution of a mixed phase structure of a positive electrode material in the embodiment of the present application (a), and crystal structure diagrams of a layered phase and a non-layered spinel phase (b, c);
FIG. 2 is Li in the examples of the present application 1.13 Mn 0.75 O 2 The surface morphology (a), TEM and electron diffraction (b) characteristic analysis results, the scale is 200nm and 10nm respectively;
FIG. 3 is Li in the examples of the present application 1.13 Mn 0.75 O 2 A crystal structure analysis (a), a high resolution TEM crystal structure characterization (b), and a schematic of the lamellar phase and spinel phase lattice adaptation (c);
FIG. 4 is Li in the examples of the present application 1.13 Mn 0.75 O 2 Electrochemical curve comparison (a) of three materials of pure lamellar, pure spinel phase and lamellar/spinel mixed phase structure, cyclic stability of lamellar phase and mixed phase structure materials and median voltage change comparison (b, c); li (Li) 1.13 Mn 0.75 O 2 In situ XRD results (d) of the miscible structure.
Detailed Description
In recent years, lithium-rich manganese materials have received extensive attention from the academia and industry because of their high voltage, high capacity, and low cost characteristics. Conventional layered cathode materials, including lithium cobaltate LiCoO 2 And ternary cathode material Li [ Ni ] x Co y Mn 1-x-y ]O 2 (0<x<1，0<y<1) Typical layered positive electrode active materials realize capacity exertion by cation valence change and small amount of anion valence change, and reversible capacity exertion is general<200mAh g -1 Energy density is generally<800Wh kg -1 But the lithium-rich manganese anode material enables the reversible capacity to be more than or equal to 250mAh g through the effective utilization of the valence-changing reaction of anions -1 Energy density is more than or equal to 1000Wh kg -1 It becomes possible.
The molecular formula of the lithium-rich manganese material can be written as xLiMn when doped with an element y M 1-y O 2 ·(1-x)Li 2 MnO 3 Wherein M is a doping element, 0<x<1，0<y<1. From the structural point of view, the lithium-rich manganese anode material can be regarded as a solid solution structure of classical layered lithium transition metal oxide and lithium-rich lithium manganate, and is a two-phase compound uniformly mixed on the nanometer scale. That is, there are two phase structures on the nanoscale in lithium-rich manganese positive electrode materials: is LiMnO 2 The layered structure belongs to R-3m space group, sixTetragonal system in which 3a site is replaced by Li + Occupied 3b site by Mn 3+ Occupied, 6c site by O 2- Ion occupancy, reversible discharge capacity<200mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the Another structure is layered Li 2 MnO 3 Belonging to the c2/m space group, monoclinic system, wherein the 3a site is replaced by Li + Occupied 3b site is occupied by 1/3 of Li + And Mn of 2/3 4+ Occupied, 6c site by O 2- Ion occupation, reversible capacity is more than or equal to 459mAh g -1 . In combination, the lithium-rich manganese anode material is in the range of 2.0-4.8V vs. Li/Li due to the special structure and the positive-negative ion valence-changing electrochemical reaction process + Can exert more than 300mAh g in the interval range -1 Is a function of the capacity of the battery.
Although the lithium-rich manganese anode material has the great advantages of high capacity, high voltage and low cost, the disadvantages of poor conductivity, low capacity utilization rate and poor cycle stability limit the industrialized application of the material. Research shows that the capacity/voltage change mechanism of the lithium-rich manganese anode material is an atomic participation and has a complex process with sequential tendency, and in the first-circle charging process, li is generated successively + From LiMn y M 1-y O 2 Is out of Li layer of (2) + From Li 2 MnO 3 Is extracted from Li layer and Mn layer to generate Li 2 O process; at the same time accompany Li + Is out of, li 2 MnO 3 Oxygen vacancies are formed in the lattice oxygen framework, indicating that some of the metal ions will also migrate inward, resulting in an irreversible phase change of the lattice framework. In the subsequent discharge process, part of Li is reduced due to the reduction of oxygen vacancies + Cannot be re-embedded in the bulk phase, resulting in a significant capacity loss during the first charge and discharge. During the subsequent charge and discharge processes, the lithium-rich manganese positive electrode material exhibits severe capacity and voltage decay due to the oxygen vacancy generation/disappearance and gradual increase of the phase change of the crystal structure.
In summary, the capacity and voltage attenuation of the lithium-manganese-rich cathode material originate from the oxygen valence shift and the oxygen migration process to form oxygen vacancies, so that if oxygen migration inhibition is realized from the structural design point of view, the structural stability of the lithium-manganese-rich material can be greatly improved, and further the cycle stability and inhibition can be improvedThe voltage is attenuated. LiMn with spinel structure features 2 O 4 The material has higher oxygen valence and oxygen migration energy barrier, such as LiMn capable of introducing spinel structure characteristics into the crystal lattice of the lithium-rich manganese positive electrode material 2 O 4 The Mn-O structural element of (C) is expected to have an oxygen migration inhibition effect.
Based on the research and development pain points and the invention conception, the application innovatively introduces a non-lamellar phase into the lithium-rich manganese material, so that the crystal structure of the lithium battery anode material has a mixed phase structure of lamellar phase and non-lamellar phase, and the lamellar phase and the non-lamellar phase are alternately arranged. In a further improvement, the mixed phase structure of the lamellar phase and the non-lamellar phase is of a nanoscale, the mixed phase structure of the lamellar phase and the non-lamellar phase is uniformly distributed in particles of the positive electrode material of the lithium battery, and the nanocrystalline domains of the lamellar phase and the non-lamellar phase are matched in lattice.
In LiMn 2 O 4 For example, the molecular formula of the novel lithium battery anode material is expressed as xLiM 2 O 4 ·(1-x)Li 2 MnO 3 . In this structure, liMn 2 O 4 The spinel phase structure does not generate oxygen valence change even at a voltage higher than 4.8V; at the same time, liMn 2 O 4 The presence of spinel phase structure also solves the problem in Li 2 MnO 3 Structural instability problems in the lamellar phase caused by oxygen valence/oxygen migration. Specifically, for Li 2 MnO 3 Lamellar phase, after partial delithiation, spontaneously migrating oxygen due to oxygen valence changes in the lattice framework due to extremely low oxygen vacancy formation energy, while in LiMn 2 O 4 In the spinel phase, the formation energy of oxygen vacancies is as high as 2.9eV and the migration energy is as high as 2.07eV, so that oxygen vacancy formation and oxygen migration hardly occur. Thus, in the process of producing LiMn 2 O 4 Spinel nanophase and Li 2 MnO 3 In the mixed phase structure composed of the lamellar nano phases, the formation of oxygen vacancies and oxygen migration are greatly inhibited, thereby greatly improving Li 2 MnO 3 Structural stability of the lamellar nanophase structure. In addition, li during charging 2 MnO 3 Volume of lamellar phase latticeExpanded, and LiMn 2 O 4 The spinel phase lattice volume contracts, whereby the lattice volume contraction and expansion of the mixed phase structure during charging cancel out, greatly reducing the volume deformation stress, which is another reason to suppress the structure decay and the generation of internal microcracks. The novel positive electrode material with the mixed phase structure of the lamellar phase and the non-lamellar phase which are distributed in the mosaic type in the crystal structure developed by the application can solve the basic scientific problem of capacity and voltage attenuation of the lithium-rich manganese-based positive electrode material due to irreversible oxygen valence change and oxygen migration from the perspective of crystal structure design, greatly improves multiplying power and circulation stability, and opens up a new paradigm of research of the lithium-rich manganese-based positive electrode material. Novel xLiMn in the present application 2 O 4 ·(1-x)Li 2 MnO 3 Lithium-rich manganese cathode material, wherein LiMn 2 O 4 Spinel nanophase and Li 2 MnO 3 The layered nano phase not only shows the characteristic of lattice structure adaptation, but also a small amount of Mn element in the structure can be replaced by other elements, including Co, ni, al, ti, zr, nb and the like, so that the lithium battery anode material with the mixed phase structure has the diversity of structure/element regulation. Based on the special mixed phase structure of the lamellar phase and the non-lamellar phase, the lithium battery anode material with the mixed phase structure realizes more than 440mAh g -1 The reversible gram capacity of the catalyst is exerted, and the catalyst has high multiplying power and cycle stability.
Besides LiMn 2 O 4 Other non-lamellar phases with high ionic and/or electronic conductivity besides spinel nanophase can also improve the structural stability of lamellar phases by increasing the activation of lattice oxygen migration and/or oxygen evolution, thereby improving the cycling stability of lithium battery positive electrode materials at high voltages > 4.5V, e.g. spinel phase Li x TM 2 O 4 Also e.g. perovskite phase LiTMO 3 Rock salt phase Li x TM 1-x O, etc., wherein 0.ltoreq.x.ltoreq.1, and TM is at least one of Mn, co, ni, al, ti, zr and Nb.
The present application is described in further detail below by way of specific examples and figures. The following examples are merely illustrative of the present application and should not be construed as limiting the present application.
Example 1
The lithium battery anode material with the mixed phase structure of the layered phase and the non-layered phase which are distributed in a mosaic manner is obtained by comprehensively adopting a solid-phase sintering and molten salt ion exchange method, namely, the layered phase and the non-layered phase are alternately arranged. The non-lamellar phase of this example is specifically a spinel phase, i.e., spinel nanocrystals. The specific preparation method of the lithium battery anode material is as follows:
step one: manganese carbonate is prepared, manganese nitrate and sodium carbonate which are weighed according to stoichiometric ratio are mixed, and stirred and reacted for 3 hours in a solution at 90 ℃ to obtain MnCO 3 A precursor; solid-phase sintering, namely mixing and grinding the prepared manganese carbonate, sodium carbonate and lithium carbonate according to the proportion of Na to Li to Mn of 0.7 to 0.3 to 0.7, and sintering for 24 hours in a muffle furnace at 550 ℃ under the air atmosphere to obtain tan powder.
Step two: ion exchange of molten salt, brown powder obtained and LiNO 3 The mixture of/LiCl (88/12) was mixed and milled in a 1:2 ratio and then treated at 280℃for 12h to effect Li/Na exchange in the crystal structure of the powder; after cooling, the mixed material is washed in deionized water and dried in a vacuum oven at 80 ℃ to obtain the nano-phase-spinel material with the structural characteristics of layered nano-phase and nano-phase mixed phase of spinel, wherein the chemical formula is Li 1.13 Mn 0.75 O 2 Is marked as LS-LMO.
Electrochemical testing: liCoO was prepared using NMP as solvent 2 Uniformly mixing @ LCAF-Spinel, carbon black and PVDF in a mass ratio of 8:1:1 to prepare a positive electrode plate, wherein the active material loading is about 5mg cm -2 . Half-cells with lithium sheets as negative electrodes were prepared using 2032 coin cells, which were operated at 2.0-4.9V (vs. Li/Li) using Celgard 2035 separator and high voltage electrolyte + ) And the cycle therebetween. Wherein the mass ratio of the high-voltage electrolyte to the LiPF 6 EMC: FEC=15:55:30. At the same time, the example also compares and tests pure lamellar phase anode material Li 2 MnO 3 Pure spinel phase positive electrode material LiMn 2 O 4 Is used for the electrochemical performance of the battery.
Fig. 1 shows a mosaic mixing distribution diagram (a) of a mixed phase structure of a positive electrode material, and crystal structure diagrams (b, c) of a lamellar phase and a non-lamellar spinel phase. The lithium-manganese-rich mixed phase structure positive electrode material of LS-LMO of the application has a crystal structure comprising spinel phase structures which are distributed in a mosaic-type interphase arrangement.
LS-LMO prepared in this example was observed using a Scanning Electron Microscope (SEM) and the results are shown in FIG. 2. The results of FIG. 2 show that the LS-LMO lithium-rich manganese cathode material synthesized in this example is represented as spherical secondary particles, the size of which is about 2 μm, the primary particle size is about 200nm, and the nanocrystalline domain sizes of the layered nanophase and the spinel nanophase are about 10nm.
The material phase structure of LS-LMO prepared by the method is analyzed by XRD and neutron diffraction, and the result shows that the lithium-rich manganese material phase structure prepared by the method is a mixed phase structure of a layered nano phase and a spinel nano phase, and high-resolution TEM results show that lattice adaptation characteristics are shown between the layered nano phase and the spinel nano phase, as shown in figure 3.
Electrochemical results show that the LS-LMO electrochemical charge-discharge curve has layered Li 2 MnO 3 And spinel phase LiMn 2 O 4 The reversible discharge capacity of LS-LCO exceeds 440mAh/g and is far higher than that of pure lamellar Li 2 MnO 3 And spinel LiMn 2 O 4 As shown in fig. 4. Compared with Li 2 MnO 3 Higher capacity, multiplying power and cycle stability are exhibited, and the voltage decay problem is greatly improved.
The in situ XRD results show that the LS-LMO integrated cell parameters are not changed during charge and discharge, due to layered Li during charge and discharge 2 MnO 3 Phase and spinel LiMn 2 O 4 The opposite trend of the phase cell parameters results in a greatly improved structural stability of the material.
Example two
The example uses perovskite phase instead of spinel phase of example one based on example one, in particularIs prepared from perovskite phase LiTi 0.5 Mn 0.5 O 3 . Wherein the lamellar phase in the present embodiment is Li 2 Mn 0.95 Ti 0.05 O 3 The non-lamellar phase being LiTi 0.5 Mn 0.5 O 3 Is a perovskite phase structure of (a). The synthesis method of the lithium battery anode material with the lamellar and non-lamellar mixed phase structure in the embodiment is as follows:
step one: synthesizing a multielement mixed precursor, and dissolving 0.01mol of tetraethyl titanate in 50mL of ethanol solution to form a solution A; dissolving 0.03mol of manganese sulfate and 0.01mol of ammonium sulfate in 200mL of deionized water to form a solution B; 0.03mol of NaOH was dissolved in 50mL of deionized water to form solution C. Solution B was heated to 60℃in a water bath, and during stirring, solutions A and C were added dropwise to solution B over 3 hours, respectively, by peristaltic pumps. After the reaction is finished, the mixed solution is heated in a water bath kettle at 60 ℃ for 3 hours. The total liquid phase reaction time was 6h. After the reaction is finished, suction filtration is carried out, and deionized water and ethanol are adopted for cleaning. And heating the obtained precursor in a muffle furnace (air atmosphere) at 500 ℃ for 6 hours to obtain the multi-component mixed precursor.
Step two: and (3) sintering at high temperature, mixing the precursors obtained in the step (I) according to the proportion of Li/(Mn+Ti) =1.15, wherein a lithium source adopts LiOH. After being uniformly mixed, the sintering condition is 800-12h, and the lithium battery anode material with layered and non-layered mixed phase structure is obtained, and the number is LPO-LMO.
Adopts TEM and XRD refinement to determine that the crystal structure of LPO-LMO is lamellar phase Li 2 Mn 0.95 Ti 0.05 O 3 Non-lamellar perovskite phase LiTi 0.5 Mn 0.5 O 3 Is a mixed phase structure of (a). Electrochemical results show that the electrochemical charge-discharge curve of the LPO-LMO has layered phase Li 2 Mn 0.95 Ti 0.05 O 3 Non-lamellar perovskite phase LiTi 0.5 Mn 0.5 O 3 Meanwhile, the reversible discharge capacity of the LPO-LMO exceeds 400mAh/g, and the LPO-LMO shows higher cycle stability.
Example III
The base of the present example in example oneOn the basis, the spinel phase of the first embodiment is replaced by the rock salt phase, and specifically the rock salt phase Li is adopted 0.1 Mn 0.5 Ni 0.4 O is used as a non-lamellar phase structure. Wherein the lamellar phase in the present embodiment is Li 2 Mn 0.9 Ni 0.1 O 3 The non-lamellar phase is Li 0.1 Mn 0.5 Ni 0.4 And O's litho-salt phase structure. The synthesis method of the lithium battery anode material with the lamellar and non-lamellar mixed phase structure in the embodiment is as follows:
step one: synthesizing a multi-component mixed precursor. 0.005mol of nickel acetate was dissolved in 50mL of an aqueous solution to form solution A; dissolving 0.03mol of manganese sulfate and 0.01mol of ammonium sulfate in 200mL of deionized water to form a solution B; 0.035mol of NaOH was dissolved in 50mL of deionized water to form solution C. Solution B was heated to 60℃in a water bath, and during stirring, solutions A and C were added dropwise to solution B over 3 hours, respectively, by peristaltic pumps. After the reaction is finished, the mixed solution is heated in a water bath kettle at 60 ℃ for 3 hours. The total liquid phase reaction time was 6h. After the reaction is finished, suction filtration is carried out, and deionized water and ethanol are adopted for cleaning. And heating the obtained precursor in a muffle furnace (air atmosphere) at 500 ℃ for 6 hours to obtain the multi-component mixed precursor.
Step two: and (5) sintering at high temperature. Mixing the precursors obtained in the step one according to the proportion of Li/(Mn+Ni) =1.25, wherein a lithium source adopts Li 2 CO 3 . After being uniformly mixed, the sintering condition is 800-24 hours, and the lithium battery anode material with layered and non-layered mixed phase structure is obtained, and the number is LRO-LMO.
Adopts TEM and XRD refinement to determine that the crystal structure of LRO-LMO is lamellar phase Li 2 Mn 0.9 Ni 0.1 O 3 And non-lamellar rock salt phase Li 0.1 Mn 0.5 Ni 0.4 Mixed phase structure of O. Electrochemical results show that the electrochemical charge-discharge curve of LRO-LMO has lamellar phase Li 2 Mn 0.9 Ni 0.1 O 3 And non-lamellar rock salt phase Li 0.1 Mn 0.5 Ni 0.4 And the charge-discharge curve characteristic of O, and the reversible discharge capacity of LRO-LMO exceeds 380mAh/g, and the cycle stability is higher.
The foregoing is a further detailed description of the present application in connection with the specific embodiments, and it is not intended that the practice of the present application be limited to such descriptions. It should be understood that those skilled in the art to which the present application pertains may make several simple deductions or substitutions without departing from the spirit of the present application, and all such deductions or substitutions should be considered to be within the scope of the present application.

Claims (10)

1. A lithium battery positive electrode material with a mixed phase structure is characterized in that: the crystal structure of the lithium battery positive electrode material is provided with a mixed phase structure of lamellar phase and non-lamellar phase, and the lamellar phase and the non-lamellar phase are alternately arranged.
2. The lithium battery positive electrode material according to claim 1, wherein: the non-lamellar phase is nanoscale;
preferably, the nanoscale is 0.5-10nm;
preferably, the mixed phase structure of the lamellar phase and the non-lamellar phase is uniformly distributed in the particles of the positive electrode material of the lithium battery;
preferably, the interphase interfacial domains of the lamellar phase and the non-lamellar phase are lattice matched.
3. The lithium battery positive electrode material according to claim 1, wherein: the non-lamellar phase comprises at least one of a spinel phase, a perovskite phase, and a rock salt phase;
preferably, the non-lamellar phase has a high ionic and/or electronic conductivity;
preferably, the non-lamellar phase inhibits the lattice oxygen migration and/or oxygen evolution process, improving the structural stability of the lamellar phase, and thus improving the cycling stability of the lithium battery positive electrode material at high voltages.
4. A lithium battery positive electrode material according to any one of claims 1 to 3, wherein: the molecular formula of the battery positive electrode active material is Li x TM y O 2 A z Wherein x is more than or equal to 1 and less than or equal to 2, y is more than or equal to 0.5 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.2, and TM is at least one of Mn, co, ni, al, ti, zr and Nb; a is F, BO 3 、SiO 4 、PO 4 And SO 4 At least one of them.
5. The lithium battery positive electrode material according to claim 4, wherein: the molecular formula of the lamellar phase is Li 2 TMO 3 Or LiTMO 2 Wherein, TM is at least one of Mn, co and Ni;
preferably, lithium and TM inversions are present in the lamellar phase;
preferably, the content of the lithium and the TM trans-site is 1-40%;
preferably, the molecular formula of the non-lamellar phase is spinel phase Li x TM 2 O 4 Perovskite phase LiTMO 3 Or rock salt phase Li x TM 1- x O, wherein x is more than or equal to 0 and less than or equal to 1, and TM is at least one of Mn, co, ni, al, ti, zr and Nb;
preferably, lithium and TM miscibility are present in the non-lamellar phase;
preferably, the content of the lithium and TM mixed row is 1% -10%.
6. A lithium battery positive electrode material according to any one of claims 1 to 3, wherein: the lithium battery anode material is large primary particles or secondary particles formed by stacking small primary particles;
the large primary particles have a size of 1-20 μm;
the secondary particles have a size of 1-20 μm;
the small primary particles have a size of 50nm to 2 μm;
preferably, the interphase interfacial domain size of the lamellar phase and the non-lamellar phase is from 0.5 to 10nm.
7. The method for preparing the positive electrode material for lithium batteries according to any one of claims 1 to 6, characterized in that: the lithium battery anode material with a mixed phase structure in which lamellar phases and non-lamellar phases are alternately arranged in a crystal structure is obtained by adopting at least one of a high-temperature sintering method, a chemical method and an electrochemical method.
8. The method of manufacturing according to claim 7, wherein: the chemical method comprises the steps of placing a sintered and synthesized lithium-rich manganese-based positive electrode material in molten salt containing at least one of lithium nitrate, lithium chloride and lithium oxide, and treating for 1-24 hours at the temperature of 250-350 ℃ to obtain a lithium battery positive electrode material with a layered phase and non-layered phase mixed phase structure;
the electrochemical method comprises the steps of mixing sintered and synthesized lithium-rich manganese-based positive electrode material, conductive carbon and polyvinylidene fluoride binder in a ratio of 90:5:5 to prepare a pole piece, and placing the pole piece in lithium salt-containing electrolyte for charging and discharging for not more than 3 circles to obtain a lithium battery positive electrode material with a layered phase and non-layered phase mixed phase structure;
preferably, the high-temperature sintering method comprises the steps of mixing and sintering multiphase mixed precursors for preparing the lithium battery anode material and lithium carbonate according to a proportion, wherein the sintering temperature is 800-1000 ℃, and the sintering time is 1-24 hours, so as to obtain the lithium battery anode material with a lamellar phase and non-lamellar phase mixed phase structure; the multiphase mixed precursor is oxide of each metal element in the lithium battery anode material.
9. Use of the lithium battery cathode material of any one of claims 1-8 in the preparation of a power battery, an energy storage battery, or a lithium ion battery for a 3C consumer electronics product, an unmanned aerial vehicle, or an electronic cigarette.
10. A lithium ion battery employing the positive electrode material for a lithium battery as claimed in any one of claims 1 to 9.
CN202211616898.6A 2022-12-15 2022-12-15 Lithium battery positive electrode material with mixed phase structure, and preparation method and application thereof Pending CN116190593A (en)

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Publication number Priority date Publication date Assignee Title
CN117080535A (en) * 2023-10-19 2023-11-17 中创新航科技集团股份有限公司 Cylindrical battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117080535A (en) * 2023-10-19 2023-11-17 中创新航科技集团股份有限公司 Cylindrical battery
CN117080535B (en) * 2023-10-19 2023-12-22 中创新航科技集团股份有限公司 Cylindrical battery

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