CN111762768A - Spinel type lithium manganate-phosphate composite cathode material and preparation method thereof - Google Patents

Spinel type lithium manganate-phosphate composite cathode material and preparation method thereof Download PDF

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CN111762768A
CN111762768A CN202010747348.2A CN202010747348A CN111762768A CN 111762768 A CN111762768 A CN 111762768A CN 202010747348 A CN202010747348 A CN 202010747348A CN 111762768 A CN111762768 A CN 111762768A
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phosphate
lithium manganate
lithium
spinel type
manganese
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CN111762768B (en
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夏晖
刘开民
夏求应
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Nanjing University of Science and Technology
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Abstract

The invention discloses a spinel type lithium manganate-phosphate composite cathode material and a preparation process thereof, wherein a lithium source compound and a manganese source compound are proportioned according to the molar ratio of Li to Mn of 0.5-0.7, and then the ratio of the phosphate compound: the mass ratio of the lithium source compound to the manganese source compound is 1-20%, and the mixture is uniformly mixed to obtain a precursor; and then performing solid-phase sintering on the precursor, and performing primary sintering to obtain the lithium manganate-phosphate composite cathode material. According to the preparation method, the spinel lithium manganate-phosphate composite cathode material is prepared by adopting one-step solid-phase co-sintering, the surfaces of lithium manganate particles are uniformly coated with a phosphate electrolyte layer with good lithium ion conductivity, and phosphate ions are uniformly doped in the lithium manganate particles, so that the diffusion coefficient of lithium ions in the lithium manganate particles can be improved while the dissolution of Mn element in the lithium manganate is inhibited, and the beneficial effects of greatly improving the cycle performance and rate capability of the lithium manganate cathode material are achieved.

Description

Spinel type lithium manganate-phosphate composite cathode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium battery anode materials, in particular to a spinel type lithium manganate-phosphate composite anode material and a preparation method thereof.
Background
The lithium ion battery becomes the first choice of a novel green energy source due to the advantages of high energy density, high working voltage, low self-discharge, long cycle life and the like, is widely applied to electronic products such as mobile phones, notebook computers, cameras and the like, and has a huge application prospect in the fields of electric automobiles, energy storage power stations and the like. Compared with lithium ion batteries in portable electronic products, lithium ion batteries in electric vehicles, energy storage power stations and the like are required to have longer service life, higher rate capability, higher safety and lower use cost.
The anode material is one of the most critical components in the lithium ion battery, and the performance of the anode material is the most critical factor for restricting the development of the lithium ion battery. Currently, lithium cobaltate, ternary materials, lithium manganate, lithium iron phosphate and the like are mainstream positive electrode materials in the market. Among them, spinel-type lithium manganate (LiMn)2O4) The method has the advantages of rich raw material resources, low price and cost, good safety performance, simple and convenient preparation method, capability of being charged and discharged quickly and the like, and is very suitable for the fields of electric automobiles, energy storage and the like which need a large amount of electric energy storage units. However, the lithium manganate material has the problems of poor cycle life, poor high-temperature performance and the like due to the Jahn-teller effect, easy dissolution of Mn in an electrolyte and the like, and further large-scale application of the lithium manganate material is greatly hindered.
At present, the modification method for the lithium manganate material mainly comprises the technologies of ion doping, morphology control, surface coating and the like.
The ion doping technology is characterized in that metal or nonmetal elements such as Al, Cr, Co, Ni, Fe, Ti, F and the like are added during the synthesis of lithium manganate so as to reduce lattice distortion of the lithium manganate in the circulation process, inhibit the occurrence of Jahn-Teller effect and improve the circulation performance, but the problem that Mn element is dissolved in electrolyte is not fundamentally solved in the process;
the morphology control technology is used for controlling the proportion of exposed crystal faces by controlling the microscopic morphology of the lithium manganate, so that the contact area of particles and electrolyte is reduced, and the dissolution of Mn in the electrolyte and other side reactions are reduced. However, the problem of Mn element dissolution cannot be solved by morphology control, and the rate of lithium manganate is influenced by the reduction of the contact area of the material and the electrolyte.
The surface coating technology is to coat a layer of metal oxide, fluorine compound, phosphate compound and the like on the surface of lithium manganate particles, so that the barrier material is in direct contact with the electrolyte, thereby reducing the dissolution of Mn in the electrolyte and improving the cycle performance and high-temperature stability of the battery. However, in the conventional surface coating method, the surface of the crystallized material particles is coated, and the lithium manganate material with high crystallinity is prepared first, and then the surface coating is performed in the second step. For example, the transition metal phosphate coated lithium ion battery composite anode material uses the transition metal phosphate to coat the lithium ion battery anode material, takes the lithium active material as an inner core, and adopts the transition metal phosphate as a coating layer, so that the dissolution and the erosion of the electrolyte to the active material are reduced, and the battery capacity is improved. However, the uniformity of the coating layer is difficult to control, the coating layer limits the transmission of ions in the charging and discharging process to a certain extent, and the rate performance of the battery is adversely affected.
As well as the prior art, the method for preparing the coated high-crystallinity lithium manganate material applied to the lithium ion battery adopts two-step sintering to realize doping and coating of a lithium manganese matrix, specifically, the first step is high-temperature sintering to obtain a high-crystallinity lithium manganate precursor with crystal particles of 0101-20 microns, the second step is coating treatment to obtain a coated product, and finally, the coated product is subjected to second high-temperature sintering to obtain a final product with a general formula of LiaMn2-b-cMbGcO4-d- eXdZeWherein M and X areDoping elements; g and Z are coating elements, and the concentration of the coating elements is in gradient distribution gradually decreasing from outside to inside; a is more than or equal to 0.9 and less than or equal to 1.2, b is more than or equal to 0 and less than or equal to 0.2, c is more than 0 and less than or equal to 0.2, d is more than or equal to 0 and less than or equal to 0.2, and e is more than or equal to 0 and less than or equal to 0.2. However, the secondary sintering treatment mode is to coat the high-crystallinity lithium manganate precursor prepared in the first step, and the uniformity of the surface of the high-crystallinity lithium manganate precursor obtained by the first sintering is difficult to control, so that the coating is still uneven, and the rate performance of the battery is affected.
The ALD technique developed in recent years has a problem that the cost is high and mass production is difficult, although the coating can be uniformly performed on the surface of lithium manganate.
Disclosure of Invention
The first purpose of the invention is to provide a spinel type lithium manganate-phosphate composite cathode material. In the material, the surfaces of lithium manganate particles are uniformly coated with phosphate electrolyte layers with good lithium ion conductivity, and phosphate ions are doped in the lithium manganate particles, so that the dissolution of Mn element in lithium manganate is inhibited, and simultaneously, the diffusion coefficient of lithium ions in the lithium manganate particles can be effectively improved, thereby greatly improving the cycle performance and rate performance of the lithium manganate anode material.
The second purpose of the invention is to provide a preparation method of the lithium manganate-phosphate composite cathode material. According to the method, the lithium manganate positive electrode material with the surface coated with phosphate electrolyte and the interior doped with phosphate ions is obtained by a one-step solid-phase co-sintering method, and the lithium manganate positive electrode material has the advantages of good cycle performance, rate capability and the like. Compared with the prior two-step method of firstly preparing the lithium manganate crystalline material and then coating the surface, the one-step co-phase sintering forming process has relatively simple control process, and after uniform mixing, the processes of temperature rise, heat preservation and temperature reduction are required to be controlled, the two-time sintering or the sintering/wrapping process is not required to be controlled, so that the complexity is reduced, the process is shortened and simplified, the uniformity of the coating layer is obviously improved, and the modification effect is obvious. In addition, the lithium manganate composite material with high crystallinity can be obtained at a lower sintering temperature by adopting the method. The method has low cost, easy operation and control and easy industrial production.
According to a first aspect of the invention, a preparation process of a spinel type lithium manganate-phosphate composite cathode material is provided, which comprises the following steps:
the method comprises the following steps of proportioning a lithium source compound and a manganese source compound according to the molar ratio of Li to Mn of 0.5-0.7, and then mixing the components according to the weight ratio of a phosphate compound: the mass ratio of the lithium source compound to the manganese source compound is 1-20%, and the lithium source compound and the manganese source compound are uniformly mixed to obtain a precursor of the lithium manganate-phosphate composite positive electrode material;
and then performing solid-phase sintering on the precursor at 600-800 ℃, and performing primary sintering to obtain the lithium manganate-phosphate composite cathode material.
Preferably, the manganese source compound is one or more of manganese dioxide, manganous oxide, manganous tetroxide, manganese monoxide, manganese oxalate, manganese acetate, manganese nitrate, manganese citrate and manganese gluconate.
Preferably, the lithium source compound is one or more of lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate and lithium citrate.
Preferably, the phosphate compound is one or more of lithium dihydrogen phosphate, lithium phosphate, ammonium dihydrogen phosphate, ammonium hypophosphite, ammonium phosphate, sodium dihydrogen phosphate, sodium hypophosphite, sodium phosphate, potassium hypophosphite, potassium dihydrogen phosphate, potassium phosphate, magnesium phosphate and aluminum phosphate.
Preferably, the temperature of the solid-phase sintering is 600-800 ℃, and the heat preservation time is 2-15 h. In a particularly optional embodiment, the temperature rise rate is 1-15 ℃/min and the temperature drop rate is 1-15 ℃/min.
Preferably, the spinel type lithium manganate-phosphate composite cathode material prepared by the invention has a reversible specific capacity of 120mAh/g under a current of 1C (1C: 148 mA/g). And, when the charge-discharge current is increased to 20C, the reversible specific capacity is 95 mAh/g. It is particularly preferred that over 1000 cycles at 1C magnification, over 82% of the initial capacity is retained. Particularly preferably, the spinel type lithium manganate-phosphate composite cathode material maintains more than 83% of the initial capacity after 800 cycles at the rate of 1C.
The object of the second aspect of the invention is also to provide a spinel type lithium manganate-phosphate composite cathode material prepared according to the aforementioned method.
According to the preparation method of the spinel lithium manganate composite material, provided by the scheme of the invention, the phosphate is added into the lithium manganate precursor, and then the lithium manganate precursor is subjected to simple one-step co-sintering, so that the lithium manganate composite positive electrode material with the coating-doping co-action can be obtained, and compared with the method of simply doping heterogeneous elements in lithium manganate, the method not only can inhibit the Jahn-Teller effect, but also can solve the problem of the dissolution of Mn elements in electrolyte. Meanwhile, compared with the method of preparing crystalline phase lithium manganate firstly and then coating other materials on the surface of the crystalline phase lithium manganate, the method can solve the problem of non-uniformity caused by secondary coating on the surface of the crystalline phase lithium manganate. The one-step co-sintering method has simple material preparation process and obvious modification effect. In addition, phosphate is directly added into the precursor, so that the crystallization temperature of the lithium manganate can be effectively reduced, and a lithium manganate positive electrode material with high crystallinity can be obtained at a lower temperature (compared with the traditional coating process), and the consistency is good.
Compared with the existing material, the invention has the following advantages and beneficial effects:
according to the spinel lithium manganate composite material provided by the invention, through one-time solid-phase co-firing forming, not only can the uniform coating of a phosphate electrolyte layer on the surfaces of lithium manganate particles be realized, but also phosphate radicals can be doped in the lithium manganate particles, so that the dissolution of Mn and the side reaction of an electrolyte on the surfaces of lithium manganate are effectively inhibited, and the migration rate of lithium ions in lithium manganate is improved. The prepared spinel lithium manganate composite cathode material has excellent cycle life and rate capability, for example, the material has a reversible specific capacity of 120mAh/g under the current of 1C (148 mA/g), the reversible specific capacity of 95mAh/g is still obtained when the charging and discharging current is increased to 20C, and 82% of the initial capacity can be still maintained after 1000 cycles under the rate of 1C.
It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below can be considered as part of the inventive subject matter of this disclosure unless such concepts are mutually inconsistent. In addition, all combinations of claimed subject matter are considered a part of the presently disclosed subject matter.
The foregoing and other aspects, embodiments and features of the present teachings can be more fully understood from the following description taken in conjunction with the accompanying drawings. Additional aspects of the present invention, such as features and/or advantages of exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of specific embodiments in accordance with the teachings of the present invention.
Drawings
The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is an XRD phase diagram of the sample obtained in example 1.
FIG. 2 is an SEM photograph of a sample obtained in example 1
FIG. 3 is a TEM image, STEM and corresponding EDS element distribution diagram of the sample obtained in example 1
FIG. 4 is a graph showing the electrochemical cycle performance of the sample obtained in example 1.
FIG. 5 is a graph showing the electrochemical rate performance of the sample obtained in example 1.
Fig. 6 is an XRD pattern of the sample obtained in comparative example 1.
Fig. 7 is an SEM image of the sample obtained in comparative example 1.
Fig. 8 is a graph of electrochemical cycle performance test of the sample obtained in comparative example 1.
Fig. 9 is a graph of electrochemical rate performance test of the sample obtained in comparative example 1.
Fig. 10 is an XRD pattern of the sample obtained in comparative example 2.
Fig. 11 is an SEM image of the sample obtained in comparative example 2.
Fig. 12 is a graph showing electrochemical cycle performance test of the sample obtained in comparative example 2.
Fig. 13 is a graph of electrochemical rate performance test of the sample obtained in comparative example 2.
Fig. 14 is an XRD pattern of the sample obtained in comparative example 3.
FIG. 15 is a graph comparing the cycle performance and rate performance of each example and comparative example.
Detailed Description
In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.
In this disclosure, aspects of the present invention are described with reference to the accompanying drawings, in which a number of illustrative embodiments are shown. Embodiments of the present disclosure are not necessarily intended to include all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in greater detail below, may be implemented in any of numerous ways, as the disclosed concepts and embodiments are not limited to any one implementation. In addition, some aspects of the present disclosure may be used alone, or in any suitable combination with other aspects of the present disclosure.
The invention generally provides a spinel type lithium manganate-phosphate composite cathode material and a preparation method thereof, belonging to the preparation of a lithium ion battery cathode material, wherein a lithium manganate precursor (a manganese source compound and a lithium source compound) is uniformly mixed with phosphate in a certain mass proportion, and then the mixture is prepared by one-step solid-phase co-sintering at a relatively low temperature. In the material, the surfaces of lithium manganate particles are uniformly coated with phosphate electrolyte layers with good lithium ion conductivity, and phosphate ions are uniformly doped in the lithium manganate particles, so that the dissolution of Mn element in lithium manganate is inhibited, and meanwhile, the diffusion coefficient of lithium ions in the lithium manganate particles can be effectively improved, thereby achieving the beneficial effects of greatly improving the cycle performance and rate capability of the lithium manganate anode material.
In the following, we will combine specific examples and comparative examples, and test procedures thereof, to more clearly describe exemplary implementations of various aspects of the present invention.
The electrochemical test patterns of the samples obtained in examples 1 to 6 and comparative examples 1 to 3 below were: the material, a conductive agent (carbon black) and a binder (polyvinylidene fluoride PVDF) are mixed according to the weight ratio of 80 to 10 to prepare slurry, then the slurry is coated on an aluminum foil, and the aluminum foil is dried and compacted in a vacuum oven to prepare the electrode plate.
And preparing the electrochemical performance of the button cell test material by using an electrode plate as a working electrode, a lithium plate counter electrode and 1M LiPF6 dissolved in Ethyl Carbonate (EC) and diethyl carbonate (DEC) (volume ratio is 1:1) as electrolyte.
The test voltage interval is 3-4.5V, and the current density 1C is 148 mA/g.
Example 1
(1) According to the mol ratio of LiOH to MnCO3Weighing LiOH and MnCO at a ratio of 1.1: 23Then weighing LiOH and MnCO37% of sodium dihydrogen phosphate in total mass. Putting the raw materials into a polyurethane ball milling tank, adding ethanol with the same mass, and using agate balls as milling balls, wherein the mass ratio of the agate balls to the raw materials is 2: 1, and ball milling and mixing for 8 hours by using a ball mill at the speed of 250 r/min. And naturally drying at room temperature, and removing the agate balls to obtain the lithium manganate composite material precursor.
(2) And (3) putting the precursor into a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, preserving the temperature for 10h, cooling to room temperature at the speed of 5 ℃/min, and taking out to obtain the lithium manganate-lithium sodium phosphate composite cathode material, wherein the lithium sodium phosphate is doped and coated on the surface of lithium manganate particles with a spinel structure.
Fig. 1 is an X-ray diffraction (XRD) pattern of the obtained sample, and it can be seen that the main phase of the sample is lithium manganate having a spinel structure. In addition, a small amount of NaLi was observed in the XRD phase diagram of the sample2PO4Is present. NaLi2PO4As the solid electrolyte material used by the invention, the coating of the solid electrolyte material on the surface of lithium manganate particles can inhibit the dissolution of Mn in lithium manganate and the side reaction of electrolyte on the surface of lithium manganate, and is beneficial to improving the cycling stability and rate capability of the lithium manganate anode. Due to the addition and doping of phosphate, lithium manganate can obtain extremely high crystallinity at lower sintering temperature of 600 DEG C. FIG. 2 is a Scanning Electron Micrograph (SEM) of the resulting sample, which is NaLi2PO4Coating large particles consisting of uniform primary particles. FIG. 3 is a TEM image, STEM image and corresponding EDS elemental distribution chart of the obtained sample, and it can be seen that the obtained sample is a large particle composed of small particles of 50 to 100 nm. The HRTEM image of the particles has obvious lattice stripes of (111) planes of the lithium manganate, and the obtained lithium manganate has good crystallinity. Also, NaLi was observed on the surface of the particles to a thickness of about 5nm2PO4The crystal lattice fringes of (211) indicate that the surfaces of the lithium manganate particles have NaLi2PO4And (4) uniformly coating the layer. The STEM graph and the corresponding EDS elemental distribution chart in fig. 3 show that Na and P are uniformly among Mn and O elements, respectively, and the surface phosphate is uniformly doped into the interior of the lithium manganate particles.
Fig. 4 is a graph of the cycle performance of the obtained sample after being made into an electrode plate, and it can be seen that the composite positive electrode can still maintain 82% of the initial capacity after being cycled for 1000 cycles under the charging and discharging current of 1C at room temperature. Fig. 5 is a graph of rate capability of a composite positive electrode having a specific capacity of 120mAh/g at a current density of 1C, yet exhibiting a specific capacity of up to 95mAh/g at a high current density of 20C.
Example 2
(1) In molar ratio of Li2CO3∶MnO2Weighing Li 1.05: 42CO3And MnO2Then weighing the occupied Li2CO3And MnO25% of lithium hypophosphite by mass. Putting the raw materials into a polyurethane ball milling tank, adding ethanol with the same mass, and using agate balls as milling balls, wherein the mass ratio of the agate balls to the raw materials is 2: 1, and ball milling and mixing for 8 hours by using a ball mill at the speed of 250 r/min. And naturally drying at room temperature, and removing the agate balls to obtain the lithium manganate composite material precursor.
(2) And (3) putting the precursor into a muffle furnace, heating to 700 ℃ at the speed of 5 ℃/min, preserving the temperature for 10h, cooling to room temperature at the speed of 2 ℃/min, and taking out to obtain the lithium manganate-lithium phosphate composite cathode material. And doping and coating lithium phosphate on the surfaces of the lithium manganate particles with the spinel structure.
The sample prepared in this example was subjected to electrochemical performance test. The test results were as follows: the composite positive electrode has an initial specific capacity of 124mAh/g at a current density of 1C, and still shows a specific capacity of up to 92mAh/g at a high current density of 20C, and still can maintain 83% of the initial capacity after 900 cycles of charge and discharge current of 1C.
Example 3
(1) According to the mol ratio of LiOH to MnO21.15: 2, then weighing LiOH and MnO27% of total mass of ammonium hypophosphite (NH)4H2PO2). Putting the raw materials into a polyurethane ball milling tank, adding ethanol with the same mass, and using agate balls as milling balls, wherein the mass ratio of the agate balls to the raw materials is 2: 1, and ball milling and mixing for 8 hours by using a ball mill at the speed of 250 r/min. And naturally drying at room temperature, and removing the agate balls to obtain the lithium manganate composite material precursor.
(2) And (3) putting the precursor into a muffle furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 15h, cooling to room temperature at the speed of 5 ℃/min, and taking out to obtain the lithium manganate-lithium phosphate composite cathode material. And doping and coating lithium phosphate on the surfaces of the lithium manganate particles with the spinel structure.
The sample prepared in this example was subjected to electrochemical performance test. The test results were as follows: the composite positive electrode has an initial specific capacity of 117mAh/g at a current density of 1C, yet still exhibits a specific capacity of up to 87mAh/g at a high current density of 20C, and still maintains 81% of the initial capacity after 900 cycles at a charge and discharge current of 1C.
Example 4
(1) According to the mol ratio of LiOH to Mn (CH)3COO)21.15: 2, then weighing LiOH and Mn (CH)3COO)28% of total mass of ammonium hypophosphite (NH)4H2PO2). Dissolving the raw materials in water, stirring in a water bath at 70 ℃ to obtain sol, and drying in an oven to obtain the lithium manganate composite material precursor.
(2) And (3) putting the precursor into a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, preserving the temperature for 15h, cooling to room temperature at the speed of 5 ℃/min, and taking out to obtain the lithium manganate-lithium phosphate composite cathode material. And doping and coating lithium phosphate on the surfaces of the lithium manganate particles with the spinel structure.
The sample prepared in this example was subjected to electrochemical performance test. The test results were as follows: the composite positive electrode has an initial specific capacity of 118mAh/g at a current density of 1C, yet still exhibits a specific capacity of up to 85mAh/g at a high current density of 20C, and still maintains 83% of the initial capacity after 800 cycles at a charge-discharge current of 1C.
Example 5
(1) In molar ratio CH3COOLi∶Mn(CH3COO)21.15: 2, then weighing CH3COOLi and Mn (CH)3COO)210% of potassium dihydrogen phosphate in total mass. Dissolving the raw materials in water, stirring in a water bath at 70 ℃ to obtain sol, and drying in an oven to obtain the lithium manganate composite material precursor.
(2) And (3) putting the precursor into a muffle furnace, heating to 700 ℃ at the speed of 5 ℃/min, preserving the temperature for 15h, cooling to room temperature at the speed of 5 ℃/min, and taking out to obtain the lithium manganate-lithium potassium phosphate composite cathode material. The lithium potassium phosphate is doped and coated on the surface of the lithium manganate particles with the spinel structure.
The sample prepared in this example was subjected to electrochemical performance test. The test results were as follows: the composite positive electrode has an initial specific capacity of 116mAh/g at a current density of 1C, yet still exhibits a specific capacity of up to 82mAh/g at a high current density of 20C, and still maintains 85% of the initial capacity after 800 cycles at a charge-discharge current of 1C.
Example 6
(1) In molar ratio of Li2C2O4∶Mn(CH3COO)21.3: 4, then weighing Li2C2O4And Mn (CH)3COO)2Ammonium phosphate in a total mass of 9%. Dissolving the raw materials in water, stirring in a water bath at 70 ℃ to obtain sol, and drying in an oven to obtain the lithium manganate composite material precursor.
(2) And (3) putting the precursor into a muffle furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 15h, cooling to room temperature at the speed of 5 ℃/min, and taking out to obtain the lithium manganate-lithium phosphate composite cathode material. And doping and coating lithium phosphate on the surfaces of the lithium manganate particles with the spinel structure.
The sample prepared in this example was subjected to electrochemical performance test. The test results were as follows: the composite positive electrode has an initial specific capacity of 125mAh/g at a current density of 1C, yet still exhibits a specific capacity of up to 84mAh/g at a high current density of 20C, and still retains 84% of the initial capacity after 800 cycles at a charge-discharge current of 1C.
Comparative example 1
(1) The procedure is as in step (1) of example 1, with a molar ratio of LiOH: MnCO3Weighing LiOH and MnCO at a ratio of 1.1: 23Putting the mixture into a polyurethane ball milling tank, adding ethanol with the same mass, using agate balls as milling balls, wherein the mass ratio of the agate balls to the raw materials is 2: 1, and carrying out ball milling and mixing for 8 hours by using a ball mill at the speed of 250 r/min. And naturally drying at room temperature, and removing the agate balls to obtain the lithium manganate precursor.
(2) Putting the precursor into a muffle furnace according to the method of the step (2) in the embodiment 1, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 10h, cooling to room temperature at the speed of 5 ℃/min, and taking out to obtain the pure-phase spinel lithium manganate material.
In order to compare with the lithium manganate composite cathode material provided by the invention, the pure-phase lithium manganate which is not doped and coated is prepared in the comparative example, and XRD and SEM detection is carried out on the obtained sample. Fig. 6 and 7 are XRD and SEM images of the obtained sample, respectively, and it can be seen that the prepared lithium manganate is pure phase, has no other impurity phase, has higher crystallinity, and has relatively larger particle size. The cycle performance of the positive electrode prepared in comparative example 1 is shown in fig. 8, and the capacity retention rate of the positive electrode is only 80% after the positive electrode is cycled for 300 cycles at a charge and discharge current of 1C at room temperature. It can be seen from the rate performance graph of fig. 9 that the specific capacity of the positive electrode at 1C rate is 105mAh/g, while the specific capacity at 20C high rate is only 18 mAh/g. This comparative example shows significantly poorer cycle life and rate performance than examples 1-6, and requires a higher heat treatment temperature.
Comparative example 2
(1) The procedure is as in step (1) of example 1, with a molar ratio of LiOH: MnCO3Weighing LiOH and MnCO at a ratio of 1.1: 23Putting the mixture into a polyurethane ball milling tank, adding ethanol with the same mass, using agate balls as milling balls, wherein the mass ratio of the agate balls to the raw materials is 2: 1, and carrying out ball milling and mixing for 8 hours by using a ball mill at the speed of 250 r/min. And naturally drying at room temperature, and removing the agate balls to obtain the lithium manganate precursor. Putting the precursor into an air atmosphere reaction furnace according to the method in the step (2) of the embodiment 1, heating to 800 ℃ at the speed of 5 ℃/min, preserving the temperature for 10 hours, cooling to room temperature at the speed of 2 ℃/min, and taking out to obtain the pure-phase spinel lithium manganate material.
(2) Weighing a proper amount of the obtained pure-phase spinel lithium manganate material, weighing lithium dihydrogen phosphate accounting for 7% of the mass of the pure-phase spinel lithium manganate material and lithium hydroxide with the molar ratio of the lithium dihydrogen phosphate to the lithium hydroxide being 1:2, mixing the materials in an aqueous solution, magnetically stirring the mixture for 2 hours, and drying the mixture to obtain a precursor. And (3) putting the precursor into an air atmosphere reaction furnace, heating to 600 ℃ at the speed of 5 ℃/min, preserving the temperature for 1h, cooling to room temperature at the speed of 5 ℃/min, and taking out to obtain the lithium manganate positive electrode material coated with lithium phosphate.
In order to compare with the lithium manganate composite anode prepared by one-step in-situ co-firing, the lithium manganate precursor is prepared by a two-step method, then the lithium phosphate surface coating is carried out, so that the lithium manganate composite anode coated by the lithium phosphate is obtained, and XRD and SEM representation is carried out on the sample. FIG. 10 is an XRD pattern of the obtained sample, which has a main phase of spinel lithium manganate phase and high crystallinity. In addition, the presence of a partial lithium phosphate phase was observed in XRD, indicating that lithium phosphate had coated on the lithium manganate particles. Fig. 11 is an SEM image of the resulting sample, and it can be seen that the surface of the particles of the resulting sample is rougher than the surface of the pure lithium manganate of fig. 6, further indicating that lithium phosphate has been coated on the surfaces of the lithium manganate particles. The cycle performance of the positive electrode prepared in comparative example 2 is shown in fig. 12, and the capacity retention rate of the positive electrode after 700 cycles of charge and discharge current at 1C at room temperature is 81%. Fig. 13 is a graph of rate performance of the resulting samples, and it can be seen that the specific capacity of the positive electrode was 120mAh/g at 1C rate, and 72mAh/g at 20C high rate. This comparative example shows relatively poorer cycle life and rate performance than examples 1-6.
Comparative example 3
(1) The procedure is as in step (1) of example 1, with a molar ratio of LiOH: MnCO3Weighing LiOH and MnCO at a ratio of 1.1: 23Putting the mixture into a polyurethane ball milling tank, adding ethanol with the same mass, using agate balls as milling balls, wherein the mass ratio of the agate balls to the raw materials is 2: 1, and carrying out ball milling and mixing for 8 hours by using a ball mill at the speed of 250 r/min. And naturally drying at room temperature, and removing the agate balls to obtain the lithium manganate precursor.
And (3) putting the precursor into an air atmosphere reaction furnace according to the method in the step (2) of the embodiment 1, heating to 600 ℃ at the speed of 5 ℃/min, preserving the temperature for 10 hours, cooling to room temperature at the speed of 5 ℃/min, and taking out to obtain the pure-phase spinel lithium manganate material.
In order to highlight that the lithium manganate composite anode prepared by in-situ co-firing can reduce the sintering temperature, the lithium manganate pure-phase anode material is prepared by adopting the same sintering temperature in the comparative example, and the prepared sample is subjected to XRD detection. Fig. 14 is an XRD chart of the obtained sample, and it can be seen that the degree of crystallization of the obtained lithium manganate sample at a lower sintering temperature of 600 ℃ is weaker and the main peak around 18 ℃ is significantly lower due to no addition of phosphate, which indicates that phosphate contributes to lithium manganate crystallization and reduces the heat treatment temperature in the lithium manganate composite positive electrode provided by the present invention. The sample prepared in this example was subjected to electrochemical performance test. The test results were as follows: has an initial specific capacity of 114mAh/g at a current density of 1C, and a specific capacity of only 10mAh/g at a high current density of 20C, and maintains 78% of the initial capacity after cycling for 200 cycles at a charge and discharge current of 1C.
In order to illustrate the advantages of the invention in reducing the sintering temperature of lithium manganate and improving the cycle life and rate capability, we specifically compare the sintering temperature, cycle performance and comparison performance of each example and comparative example in the table of fig. 15, and it can be seen that in the examples of the invention, the composite cathode material formed by one-time co-sintering adopted in the invention has beneficial effects and matching in sintering temperature and battery performance.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.

Claims (9)

1. A preparation process of a spinel type lithium manganate-phosphate composite cathode material is characterized by comprising the following steps:
the method comprises the following steps of proportioning a lithium source compound and a manganese source compound according to the molar ratio of Li to Mn of 0.5-0.7, and then mixing the components according to the weight ratio of a phosphate compound: the mass ratio of the lithium source compound to the manganese source compound is 1-20%, and the lithium source compound and the manganese source compound are uniformly mixed to obtain a precursor of the lithium manganate-phosphate composite positive electrode material;
and then performing solid-phase sintering on the precursor in the previous step, wherein the temperature of the solid-phase sintering is 600-800 ℃, the heat preservation time is 2-15 hours, and performing primary sintering to obtain the lithium manganate-phosphate composite cathode material, wherein the phosphate is at least partially doped and coated on the surfaces of lithium manganate particles.
2. The process for preparing the spinel type lithium manganate-phosphate composite cathode material of claim 1, wherein the manganese source compound is one or more of manganese dioxide, manganese sesquioxide, manganous tetroxide, manganese monoxide, manganese oxalate, manganese acetate, manganese nitrate, manganese citrate and manganese gluconate.
3. The process for preparing a spinel type lithium manganate-phosphate composite positive electrode material according to claim 1, wherein said lithium source compound is one or more of lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate and lithium citrate.
4. The process for preparing the spinel type lithium manganate-phosphate composite positive electrode material of claim 1, wherein the phosphate compound is one or a mixture of more of lithium dihydrogen phosphate, lithium phosphate, ammonium dihydrogen phosphate, ammonium hypophosphite, ammonium phosphate, sodium dihydrogen phosphate, sodium hypophosphite, sodium phosphate, potassium hypophosphite, potassium dihydrogen phosphate, potassium phosphate, magnesium phosphate and aluminum phosphate.
5. The preparation process of the spinel type lithium manganate-phosphate composite cathode material according to claim 1, wherein in the solid-phase sintering process, the temperature rising rate is 1-15 ℃/min, and the temperature lowering rate is 1-15 ℃/min.
6. The spinel type lithium manganate-phosphate composite cathode material prepared by the preparation process of the spinel type lithium manganate-phosphate composite cathode material according to any one of claims 1 to 5, is characterized in that the spinel type lithium manganate-phosphate composite cathode material has a reversible specific capacity of 120mAh/g at a current of 1C.
7. The spinel type lithium manganate-phosphate composite positive electrode material of claim 6, wherein said spinel type lithium manganate-phosphate composite positive electrode material has a reversible specific capacity of 95mAh/g when a charge-discharge current is increased to 20C.
8. The spinel type lithium manganate-phosphate composite positive electrode material of claim 6, wherein said spinel type lithium manganate-phosphate composite positive electrode material retains more than 82% of initial capacity after 1000 cycles at 1C rate.
9. The spinel type lithium manganate-phosphate composite positive electrode material of claim 6, wherein said spinel type lithium manganate-phosphate composite positive electrode material maintains more than 83% of initial capacity after 800 cycles at 1C rate.
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