CN111755671B - Positive electrode material and lithium ion secondary battery - Google Patents
Positive electrode material and lithium ion secondary battery Download PDFInfo
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Abstract
Provided are a positive electrode material and a lithium ion secondary battery. The positive electrode material includes: the coating material is formed on at least a part of the surface of the base material. The coating material has a coefficient of thermal expansion of-4 x 10 at a temperature of 100-400K ‑6 ～4*10 ‑6 K ‑1 . The positive electrode material coated by the coating material has better structural stability, thermal stability and electrochemical performance.
Description
Technical Field
The present application relates to the field of batteries, and more particularly, to a positive electrode material and a lithium ion secondary battery.
Background
In a lithium ion secondary battery, spinel-type LiMn is used under the action of an electrolyte 2 O 4 Metal elements in (LMO) are easily solvated, so that manganese ions are dissolved, and simultaneously, particle surface damage and gas generation phenomena are caused, so that the safety performance of the lithium ion secondary battery is influenced, the service life of the lithium ion secondary battery is damaged, the lithium ion secondary battery is more serious at high temperature and high cut-off voltage, and the same phenomenon also exists in a layered positive electrode material system such as lithium-containing nickel-cobalt-manganese metal oxide (NCM).
The surface coating process is considered to be a simple and effective method for improving the performance of the anode material. And a layer of interface layer capable of conducting Li < + > is coated on the surface of the LMO to mechanically isolate the contact of the electrolyte and the LMO, so that the high-temperature storage and cycle performance of the LMO is improved.
However, under the conditions of heat generation and high temperature during charging and discharging, the conventional coating layer of the LMO material expands due to heating, and mechanical attenuation of the coating layer is accelerated, so that the mechanical isolation effect of the coating layer is reduced, the LMO/electrolyte interface is deteriorated, manganese ion dissolution is accelerated, and the cycle and high-temperature performance of the lithium ion secondary battery are deteriorated.
Disclosure of Invention
The application provides cladding material clad cathode material, this cladding material can effectively reduce the heat expansion that cathode material takes off and inlays the lithium in-process temperature rise and bring to effectively reduce the mechanical attenuation of coating, promote cathode material's interface stability, play fine alleviating effect to the decomposition of electrolyte and the corruption to cathode material simultaneously, therefore cathode material electrochemical performance under the high voltage obtains improving.
In some embodiments, the present application provides a positive electrode material comprising: a base material; and a clad material formed on at least a part of a surface of the base material; the coating material has a coefficient of thermal expansion of-4 x 10 at a temperature of 100-400K -6 ～4*10 -6 K -1 。
In some embodiments, the cladding material comprises TaO 2 F、Zn 4 B 6 O 13 、ZrMgMo 3 O 12 、CaMn 7 O 12 、Fe[Co(CN) 6 ]And N (CH) 3 ) 4 CuZn(CN) 4 At least one of (a).
In some embodiments, the ratio of the mass of the coating material to the total mass of the base material and the coating material is 0.05% to 10%.
In some embodiments, the matrix material comprises at least one of the following materials: liMn 2 O 4 ；Li(Ni x Co y Mn z )O 2 Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 11，x+y+z＝1；LiMn 2-a O 4 M a Wherein M is at least one of Li, mg, zr, al, ti, C and La, 0<a<2；Li(Ni b Co c Mn d )O 2 N e Wherein, N is at least one of Mg, zr, al, ti, ce and La, and b + c + d + e =1.
In another embodiment, the present application provides a method of preparing a positive electrode material, including: adding the coating material into the base material, grinding and mixing to obtain a mixed material; sintering the mixed material to obtain the anode material; wherein the coating material has a coefficient of thermal expansion of-4 x 10 at a temperature of 100-400K -6 ～4*10 -6 K -1 。
In some embodiments, the cladding material comprises TaO 2 F、Zn 4 B 6 O 13 、ZrMgMo 3 O 12 、CaMn 7 O 12 、Fe[Co(CN) 6 ]And N (CH) 3 ) 4 CuZn(CN) 4 At least one of (1).
In some embodiments, the temperature of the sintering is 400 ℃ to 900 ℃, the sintering is performed under an inert atmosphere, and the time of the sintering is 15 to 30 hours.
In some embodiments, the mass of the cladding material is 0.05% to 10% of the total mass of the base material and the cladding material.
In another embodiment, the present application further provides a positive electrode sheet, including: a positive current collector; and a positive electrode material disposed on the positive electrode current collector; wherein the cathode material comprises the cathode material.
In another embodiment, the present application also provides a lithium ion secondary battery comprising the above positive electrode tab.
The positive electrode material provided by the application has better structural stability, thermal stability and electrochemical performance. The coating material can effectively reduce thermal expansion caused by temperature rise in the process of lithium desorption and insertion of the cathode material, effectively reduce mechanical attenuation of the coating layer, improve interface stability of the cathode material, and simultaneously play a good role in relieving decomposition of electrolyte and corrosion of the cathode material, so that the electrochemical performance of the cathode material under high voltage is improved.
Drawings
Fig. 1 shows a scanning electron microscope image (SEM) of the positive electrode material in example 9.
FIG. 2 shows LiMnO 2 Coated LiMnO of example 9 2 Cycle profile of the prepared lithium ion secondary battery.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present application and are not intended to limit the present application in any way.
The positive electrode material of the present application includes a base material and a coating material, wherein the coating material is formed on at least a part of a surface of the base material. The matrix material may include at least one of the following materials: liMn 2 O 4 ；Li(Ni x Co y Mn z )O 2 Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z =1; liMn 2-a O 4 M a Wherein M is at least one of Li, mg, zr, al, ti, C and La, 0<a<2；Li(Ni b Co c Mn d )O 2 N e Wherein, N is at least one of Mg, zr, al, ti, ce and La, and b + c + d + e =1. For example, the matrix material includes: lithium manganate material; liNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811)、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622)、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523)、LiNi 1/3 Co 1/3 Mn 1/3 O 2 Ternary materials such as (NCM 333); a lithium cobaltate material; other metal oxides capable of lithium deintercalation, and the like.
The coating material has a coefficient of thermal expansion of-4 to 4 x 10 at a temperature of 100 to 400K -6 K -1 . In some embodiments, the clad material of the present application has a coefficient of thermal expansion of-1 x 10 at a temperature of 200-300K -6 ～3.5*10 -6 K -1 . For example, the coating material comprises TaO 2 F、Zn 4 B 6 O 13 、ZrMgMo 3 O 12 、CaMn 7 O 12 、Fe[Co(CN) 6 ]And N (CH) 3 ) 4 CuZn(CN) 4 At least one of (1).
When the anode material works under a high voltage condition, the thermal stability and the electrochemical stability of the anode material are poor, so that the electrochemical performance and the safety performance of a battery are influenced, for example, the problems of battery short circuit caused by cobalt/manganese dissolution, electrode component flatulence generated by the reaction of an anode and electrolyte and the like are solved. Compared with other coating materials, the coating material can maintain a specific structural size in a certain temperature range, and cannot expand or contract due to temperature change or environmental temperature change caused by charging and discharging. According to the method, the surface of the anode material is coated and modified by adopting a simple coating process, so that the anode material with better mechanical property is obtained. In some implementations, in the coating material, the coating material is uniformly distributed on the surface of the particles, so that the crystal structure of the surface of the particles is stabilized, and the opportunity of the anode material contacting with the electrolyte is reduced, thereby reducing the dissolution of metal ions in the anode material, further preventing the damage of the structure, and improving the electrochemical performance of the anode material.
The positive electrode material coated by the coating material provided by the application has better structural stability, thermal stability and electrochemical performance. The coating material can effectively reduce the thermal expansion caused by the temperature rise in the lithium releasing and embedding process of the anode material, effectively reduce the mechanical attenuation of the coating layer, improve the interface stability of the anode material, and simultaneously play a good role in relieving the decomposition of electrolyte and the corrosion of the anode material, so that the electrochemical performance of the anode material under high voltage is improved.
In some embodiments, the coating material has a coating amount of 0.05% to 10%. The coating amount of the coating material means a ratio of the mass of the coating material to the total mass of the base material and the coating material. In some embodiments, the coating material has a coating amount of 0.2% to 5%. As the coating amount increases, the improvement of the cycle performance of the positive electrode material gradually increases, and the high-temperature performance of the lithium ion secondary battery is also continuously improved, but when the coating amount is too high, for example, more than 10%, the improvement effect is no longer significant, and the decrease in gram capacity of the positive electrode material is also more significant. When the coating amount is less than 0.05%, the effect of improving the electrical properties of the lithium ion secondary battery is remarkably reduced due to the excessively small addition amount. And due to proper coating, the performance of the anode material can be optimized, and the anode material cannot lose large specific discharge capacity.
In addition, the present application provides a method for preparing the positive electrode material, the method comprising the steps of:
(1) Firstly, grinding a coating material until large particles which can be seen by naked eyes do not exist, and then sieving the ground coating material with a 400-mesh sieve;
(2) Adding coating material powder into the positive electrode material powder, grinding until no large particles can be seen by naked eyes, and sieving with a 400-mesh sieve to obtain mixed powder;
(3) And sintering the mixed powder at a certain temperature for a period of time to obtain the coated anode material.
The coating material used in the production method of the present application is as described above, and will not be described repeatedly. In some embodiments, the ratio of the mass of the coating material to the total mass of the base material and the coating material is 0.05% to 10%. In some embodiments, the temperature of sintering is 400 ℃ to 900 ℃. In some embodiments, the sintering is performed under an inert atmosphere. In some embodiments, the time for sintering is 15-30 hours. At lower sintering temperatures, the performance improvement is not significant, due to the less uniform distribution of the coating material; when the sintering temperature is too high, the material is over-sintered, and the capacity and the cycle performance of the positive electrode material are also reduced. Meanwhile, the sintering atmosphere also has a certain influence on the performance of the coating material, because when the coating material is sintered in the air, non-metal ions are oxidized at different degrees at high temperature, so that the particle structure is damaged, and the stability of the anode material and the safety of the lithium ion secondary battery are influenced. In addition, the sintering time may have an effect on the properties of the clad material, mainly because the sintering time may have an effect on the uniformity and stability of the clad material.
In addition, the sintering process can obtain the anode materials with different coating amounts by adjusting the technical parameters such as reaction temperature, coating amount and the like, and is applied to various working conditions. Therefore, the reaction conditions are easy to control, the process is mature, the synthesized coated positive electrode material has better performance and stable particle structure, and the electrochemical performance and safety performance of the lithium ion secondary battery can be effectively improved.
The embodiment of this application still provides a positive pole piece, including the anodal mass flow body and set up the anodal material on the anodal mass flow body, anodal material includes above anodal material. For the positive electrode collector, for example, aluminum foil and nickel foil may be used, however, other positive electrode collectors commonly used in the art may be used.
The application also provides a lithium ion secondary battery comprising the positive pole piece. The lithium ion secondary battery comprises a positive pole piece, a negative pole piece, an isolating membrane, electrolyte and the like. Wherein the separator is inserted between the positive electrode plate and the negative electrode plate.
Negative pole piece
The negative electrode tab includes a negative electrode material including a negative electrode material capable of absorbing and releasing lithium (Li) (hereinafter, sometimes referred to as "negative electrode material capable of absorbing/releasing lithium Li"). Examples of the negative electrode material capable of absorbing/releasing lithium (Li) may include carbon materials, metal compounds, oxides, sulfides, nitrides of lithium such as LiN 3 Lithium metal, metals that form alloys with lithium, and polymeric materials.
The carbon material may include low-graphitizable carbon, artificial graphite, natural graphite, mesocarbon microbeads, soft carbon, hard carbon, pyrolytic carbon, coke, glassy carbon, an organic polymer compound sintered body, carbon fiber, and activated carbon. The coke may include pitch coke, needle coke, and petroleum coke, among others. The organic polymer compound sintered body refers to a material obtained by calcining a polymer material such as a phenol plastic or furan resin at an appropriate temperature to carbonize it, and some of these materials are classified into low-graphitizable carbon or graphitizable carbon. Examples of the polymer material may include polyacetylene and polypyrrole.
Among these anode materials capable of absorbing/releasing lithium (Li), further, a material having a charge and discharge voltage close to that of lithium metal is selected. This is because the lower the charge and discharge voltage of the anode material, the easier an electrochemical device (e.g., a lithium ion secondary battery) has a higher energy density. Among them, the negative electrode material can be selected from carbon materials because their crystal structures are changed only slightly upon charging and discharging, and therefore, good cycle characteristics and large charge and discharge capacities can be obtained. Graphite is particularly preferred because it gives a large electrochemical equivalent and a high energy density.
In addition, the anode material capable of absorbing/releasing lithium (Li) may include elemental lithium metal, metal elements and semimetal elements capable of forming an alloy together with lithium (Li), alloys and compounds including such elements, and the like. In particular, they are used together with a carbon material because in this case, good cycle characteristics and high energy density can be obtained. Alloys as used herein include, in addition to alloys comprising two or more metallic elements, alloys comprising one or more metallic elements and one or more semi-metallic elements. The alloy may be in the following states solid solution, eutectic crystal (eutectic mixture), intermetallic compound and mixtures thereof.
Examples of the metallic element and the semi-metallic element may include tin (Sn), lead (Pb), aluminum (Al), indium (In), silicon (Si), zinc (Zn), antimony (Sb), bismuth (Bi), cadmium (Cd), magnesium (Mg), boron (B), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), zirconium (Zr), yttrium (Y), and hafnium (Hf). Examples of the above alloys and compounds may include those having the formula: ma s Mb t Li u And a material having the formula: ma p Mc q Md r The material of (2). In these chemical formulae, ma represents at least one of a metal element and a semimetal element capable of forming an alloy together with lithium; mb represents at least one element of metal elements and semimetal elements other than lithium and Ma; mc represents at least one element of non-metallic elements; md represents at least one element of metal elements other than Ma and semimetal elements; and s, t, u, p, q and r satisfy s > 0, t ≧ 0, u ≧ 0P is more than 0, q is more than 0 and r is more than or equal to 0.
In addition, an inorganic compound excluding lithium (Li), such as MnO, may be used in the negative electrode 2 、V 2 O 5 、V 6 O 13 NiS, and MoS.
Electrolyte solution
The lithium ion secondary battery further comprises an electrolyte, wherein the electrolyte can be one or more of a gel electrolyte, a solid electrolyte and a liquid electrolyte, and the liquid electrolyte comprises a lithium salt and a non-aqueous solvent.
The lithium salt is selected from LiPF 6 、LiBF 4 、LiAsF 6 、LiClO 4 、LiB(C 6 H 5 ) 4 、LiCH 3 SO 3 、LiCF 3 SO 3 、LiN(SO 2 CF 3 ) 2 、LiC(SO 2 CF 3 ) 3 、LiSiF 6 One or more of LiBOB and lithium difluoroborate. For example, liPF is selected as lithium salt 6 Since it can give high ionic conductivity and improve cycle characteristics.
The non-aqueous solvent may be a carbonate compound, a carboxylate compound, an ether compound, other organic solvent, or a combination thereof.
The carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluoro carbonate compound, or a combination thereof.
Examples of the chain carbonate compound are diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl Propyl Carbonate (MPC), ethyl Propyl Carbonate (EPC), methyl Ethyl Carbonate (MEC), and combinations thereof. Examples of the cyclic carbonate compound are Ethylene Carbonate (EC), propylene Carbonate (PC), butylene Carbonate (BC), vinyl Ethylene Carbonate (VEC), and combinations thereof. Examples of the fluoro carbonate compound are Fluoro Ethylene Carbonate (FEC), 1, 2-difluoroethylene carbonate, 1, 2-trifluoroethylene carbonate, 1, 2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1, 2-difluoro-1-methylethylene carbonate, 1, 2-trifluoro-2-methylethylene carbonate, trifluoromethyl ethylene carbonate, and combinations thereof.
Examples of carboxylate compounds are methyl acetate, ethyl acetate, n-propyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, γ -butyrolactone, decalactone, valerolactone, mevalonic lactone, caprolactone, methyl formate, and combinations thereof.
Examples of ether compounds are dibutyl ether, tetraglyme, diglyme, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and combinations thereof.
Examples of other organic solvents are dimethylsulfoxide, 1, 2-dioxolane, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, formamide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphate esters and combinations thereof.
Isolation film
For example, the separator includes a substrate layer and a surface treatment layer; the substrate layer is a non-woven fabric, a film or a composite film with a porous structure, and the material of the substrate layer is at least one selected from polyethylene, polypropylene, polyethylene terephthalate and polyimide. Specifically, a polypropylene porous film, a polyethylene porous film, a polypropylene nonwoven fabric, a polyethylene nonwoven fabric, a polypropylene-polyethylene-polypropylene porous composite film can be selected. At least one surface of the substrate layer is provided with a surface treatment layer, and the surface treatment layer can be a polymer layer or an inorganic layer, or a layer formed by mixing a polymer and an inorganic substance.
Electrochemical device
The positive electrode plate, the negative electrode plate, the electrolyte and the separator prepared from the positive electrode material described above can be assembled into a lithium ion secondary battery by a method commonly used in the art, wherein the positive electrode plate, the separator, the negative electrode plate and the like are sequentially wound or stacked into a bare cell, and then packaged in an aluminum plastic film for example, and then injected with the electrolyte, and after formation, packaging and testing, electrochemical performance testing and cycle performance testing are performed on the assembled lithium ion secondary battery.
It will be understood by those skilled in the art that the above-described method of manufacturing a lithium ion secondary battery is only an example. Other methods commonly used in the art may be employed without departing from the disclosure herein.
Some specific examples and comparative examples are listed below to better illustrate the present application.
Comparative example 1
(1) Preparation of positive pole piece
Mixing a base material LiMnO 2 Directly sintering the mixture for 24 hours at 800 ℃ in an inert atmosphere without coating. Then LiMnO is added 2 The positive pole piece is obtained by fully stirring and uniformly mixing acetylene black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder in an N-methyl pyrrolidone solvent system according to the mass ratio of 95.
(2) Preparation of negative electrode plate
The method comprises the following steps of (1) fully stirring and uniformly mixing the negative active material artificial graphite, the conductive agent acetylene black, the binder Styrene Butadiene Rubber (SBR) and the thickener carboxymethylcellulose sodium (CMC) in a deionized water solvent system according to a mass ratio of 96.
(3) Preparation of the separator
Polyethylene (PE) porous polymeric films were used as separators.
(4) Preparation of the electrolyte
Lithium salt LiPF 6 And (3) a nonaqueous organic solvent (ethylene carbonate (EC): diethyl carbonate (DEC): propylene Carbonate (PC): propyl Propionate (PP): vinylene Carbonate (VC)) =20: 92 as an electrolyte of the lithium ion secondary battery.
(5) Preparation of lithium ion secondary battery
And (3) sequentially stacking the positive pole piece, the isolating film and the negative pole piece, so that the isolating film is positioned between the positive pole piece and the negative pole piece to play a role of safety isolation, and winding to obtain the electrode assembly. And (4) placing the electrode assembly in a packaging shell, injecting an electrolyte and packaging to obtain the lithium ion secondary battery.
Comparative example 2
In accordance with the production method of comparative example 1, except that the matrix material used in comparative example 2 was LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523)。
Comparative example 3
The method is the same as the method for preparing the comparative example 1, except that the method for preparing the positive electrode plate in the comparative example 3 comprises the following steps:
firstly, coating material Zn 4 B 6 O 13 Grinding uniformly, and sieving with a 400-mesh sieve to obtain coating material powder. In the matrix material LiMnO 2 The coating material powder is added into the powder, the mass of the coating material accounts for 3 percent of the total mass of the base material and the coating material, and the powder is ground until no large particles can be seen by naked eyes, and then is sieved by a 400-mesh sieve without sintering, so that the cathode material is obtained. The positive electrode material, the conductive agent acetylene black and the binder polyvinylidene fluoride (PVDF) are fully stirred and uniformly mixed in an N-methyl pyrrolidone solvent system according to the mass ratio of 95.
Comparative example 4
The method is the same as the method for preparing the comparative example 1, except that the method for preparing the positive electrode plate in the comparative example 4 comprises the following steps:
firstly, coating material Al 2 O 3 Grinding uniformly, and sieving with a 400-mesh sieve to obtain coating material powder. In a matrix material LiMnO 2 The coating material powder is added into the powder, the mass of the coating material accounts for 3 percent of the total mass of the base material and the coating material, and the powder is ground until large particles which can be seen by naked eyes do not exist, and then the powder is sieved by a 400-mesh sieve, so that mixed powder is obtained. And sintering the mixed powder at 800 ℃ in an inert atmosphere for 24h to obtain the cathode material. The preparation method comprises the following steps of fully stirring and uniformly mixing a positive electrode material, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) in an N-methylpyrrolidone solvent system according to a mass ratio of 95.
Example 1
In accordance with the preparation method of comparative example 4, except that the clad material used in example 1 was Zn 4 B 6 O 13 The mass of the coating material accounts for 0.05% of the total mass of the base material and the coating material.
Example 2
In accordance with the production method of example 1, except that the proportion of the mass of the coating material in example 2 to the total mass of the base material and the coating material was 0.1%.
Example 3
In accordance with the production method of example 1, except that the proportion of the mass of the coating material in example 3 to the total mass of the base material and the coating material was 0.2%.
Example 4
In accordance with the production method of example 1, except that the proportion of the mass of the coating material in example 4 to the total mass of the base material and the coating material was 0.6%.
Example 5
In accordance with the production method of example 1, except that the mass of the coating material in example 5 accounts for 1% of the total mass of the base material and the coating material.
Example 6
In accordance with the production method of example 1, except that the proportion of the mass of the coating material in example 6 to the total mass of the base material and the coating material was 3%.
Example 7
In accordance with the production method of example 1, except that the mass of the coating material in example 7 accounts for 5% of the total mass of the base material and the coating material.
Example 8
In accordance with the production method of example 1, except that the proportion of the mass of the coating material in example 8 to the total mass of the base material and the coating material was 10%.
Example 9
In accordance with the preparation method of example 1, except that LiNi was used as the base material in example 9 0.5 Co 0.2 Mn 0.3 O 2 The mass of the coating material accounts for 3% of the total mass of the base material and the coating material.
Example 10
In accordance with the preparation method of example 6, except that the sintering temperature in example 10 was 400 ℃.
Example 11
In accordance with the preparation method of example 6, except that the sintering temperature in example 11 was 600 ℃.
Example 12
In accordance with the preparation method of example 6, except that the sintering temperature in example 12 was 900 ℃.
Example 13
In accordance with the preparation method of example 6, except that the sintering atmosphere in example 13 was air.
Example 14
In accordance with the preparation method of example 6, except that the sintering time in example 14 was 15 hours.
Example 15
In accordance with the preparation method of example 6, except that the sintering time in example 15 was 30 hours.
Example 16
In accordance with the preparation of example 6, except that TaO was used as the coating material in example 16 2 F。
Example 17
Consistent with the preparation method of example 6, except that ZrMgMo was used as the cladding material in example 17 3 O 12 。
Example 18
Consistent with the preparation of example 6, except that the coating material used in example 18 was CaMn 7 O 12 。
Example 19
In accordance with the preparation method of example 6, except that the clad material used in example 19 was Fe [ Co (CN) 6 ]。
Example 20
Preparation method of the same as example 6In agreement, except that the coating material used in example 20 was N (CH) 3 ) 4 CuZn(CN) 4 。
Example 21
In accordance with the production method of example 16, except that the mass of the covering material in example 21 accounts for 1% of the total mass of the base material and the covering material.
Example 22
In accordance with the production method of example 16, except that the proportion of the mass of the covering material in example 22 to the total mass of the base material and the covering material was 5%.
Example 23
Consistent with the preparation method of example 6, except that ZrMgMo was used as the cladding material in example 23 3 O 12 The mass of the coating material accounts for 1% of the total mass of the base material and the coating material.
Example 24
Consistent with the preparation method of example 6, except that ZrMgMo was used as the cladding material in example 24 3 O 12 The mass of the coating material accounts for 5% of the total mass of the base material and the coating material.
Example 25
In accordance with the preparation method of example 6, except that the coating material used in example 25 was Fe [ Co (CN) 6 ]The mass of the coating material accounts for 1% of the total mass of the base material and the coating material.
Example 26
In accordance with the preparation method of example 6, except that the clad material used in example 26 was Fe [ Co (CN) 6 ]The mass of the coating material accounts for 5% of the total mass of the base material and the coating material.
Next, a test procedure of the lithium ion secondary battery is explained.
(1) XRD test
The positive electrode sheets prepared in the comparative examples and examples were subjected to an X-ray diffraction (XRD) test. X-ray diffraction (XRD) is mainly used to study the crystal structure inside materials because X-rays have the same structure as that of X-raysThe crystal lattice has similar interplanar spacing wavelength and certain penetrating power, and one beam of X-ray passes through the crystal to be diffracted, and then the diffraction pattern of the X-ray is analyzed, so that the phase identification and the structural analysis can be carried out on the X-ray. Testing working conditions: cu Kalpha radiation, working current of 250mA, continuous scanning, working voltage of 40kV, scanning range of 15-70 degrees 2 theta, step length of 0.02, and scanning speed of 10 DEG min -1 。
(2) Gram volume test
The lithium ion secondary batteries of comparative examples and examples were each charged at 5 times at a constant current of 0.1C rate at normal temperature until the voltage reached 4.3V, and further charged at a constant voltage of 4.3V until the current was less than 0.05C, so that they were in a fully charged state of 4.3V. Then constant current discharge at 0.1C rate was stopped until the voltage was 3.0V.
(3) Cycle performance test
The lithium ion secondary batteries prepared in the comparative examples and examples were 5 each, and the lithium ion secondary batteries were repeatedly charged and discharged through the following steps, and the cycle capacity retention rates of the lithium ion secondary batteries were calculated.
Firstly, carrying out first charging and discharging in an environment at 25 ℃, carrying out constant-current and constant-voltage charging under a charging current of 0.1C (namely a current value of completely discharging theoretical capacity within 10 h) until the upper limit voltage is 4.3V, then carrying out constant-current discharging under a discharging current of 1C until the final voltage is 3V, and recording the discharging capacity of the first cycle; then, 100 cycles of charge and discharge were performed, and the discharge capacity at the 100 th cycle was recorded.
Cycle capacity retention ratio = (discharge capacity at 100 th cycle/discharge capacity at first cycle) × 100%.
Table 1 shows the experimental results of examples 1-9 and comparative examples 1-2.
TABLE 1
Note: the sintering temperature is 800 ℃, the sintering atmosphere is inert gas, and the sintering time is 24 hours.
As can be seen by comparing comparative document 1 with examples 1 to 8, zn was used 4 B 6 O 13 The cycle capacity retention rate of the coated lithium manganate and the lithium ion secondary battery is greatly improved, and the influence of the gram discharge capacity is small. Zn 4 B 6 O 13 The thermal expansion coefficient is 3.5 x 10-6K in the temperature range of 100-400K -1 And the coating layer formed by the coating material hardly has thermal expansion under the charging and discharging heat generating condition, so that the mechanical attenuation of the coating layer in the charging and discharging process is slowed down, and the stability of the interface between lithium manganate and electrolyte is improved.
Comparing comparative example 2 with example 9, it can be seen that the retention rate of the cycle capacity of the lithium ion secondary battery prepared from the positive electrode material coated with the coating material is greatly improved, and the gram-discharge capacity is not affected substantially.
When the coating amount of the coating material is 0.05-10%, the improvement of the lithium manganate cycle performance is gradually increased along with the increase of the coating amount, and the high-temperature performance of the lithium ion secondary battery is also continuously improved. The coating layer positioned on the surface area of the particles effectively reduces the contact between the material and electrolyte, reduces the dissolution of manganese in the lithium manganate material, further prevents the damage of a spinel structure, and improves the electrochemical performance of the anode material. Zn 4 B 6 O 13 The coating has the same effect on the ternary material, the cycle performance is also improved, and the corrosion of HF to the anode material is prevented, so that the cycle performance of the anode material under high voltage is improved.
Table 2 shows the experimental results of comparative example 3, example 6 and 10-15.
TABLE 2
| Sintering temperature | Sintering atmosphere | Sintering time/h | 0.1C discharge gram volume mAh- g | Retention ratio of circulating capacity% | |
| Example 6 | 800℃ | Inert gas | 24 | 109 | 80.8 |
| Example 10 | 400℃ | Inert gas | 24 | 108 | 75.1 |
| Example 11 | 600℃ | Inert gas | 24 | 108 | 78.3 |
| Example 12 | 900℃ | Inert gas | 24 | 105 | 76.7 |
| Example 13 | 800℃ | Air (a) | 24 | 105 | 75.2 |
| Example 14 | 800℃ | Inert gas | 15 | 108 | 75.9 |
| Example 15 | 800℃ | Inertia of | 30 | 106 | 79.7 |
| Comparative example 3 | \ | \ | \ | 115 | 65.3 |
Note: the coating is Zn 4 B 6 O 13 The coating amount is 3 percent, and the anode material is LiMnO 2 。
From the experimental results of comparative example 3 and examples 10 to 15, it can be seen that, when the sintering temperature ranges from 400 ℃ to 900 ℃, the gram-discharge capacity and the cycle capacity retention rate of the lithium ion secondary battery both show a tendency of increasing first and then decreasing as the sintering temperature gradually increases. Meanwhile, the sintering atmosphere also has a certain influence on the performance of the coating material, because when the coating material is sintered in the air, non-metal ions may be oxidized to different degrees at high temperature, so that the particle structure is damaged, and the stability of the anode material and the safety of the lithium ion secondary battery are affected. In addition, the sintering time also has a certain influence on the performance of the coating material, mainly because the sintering time has a certain influence on the uniformity and stability of the coating layer.
Table 3 shows the experimental results of comparative example 4, example 6 and 16-26.
TABLE 3
| Cladding material | Coating amount | 0.1C discharge gram volume mAh- g | Retention ratio of circulating capacity% | |
| Example 6 | Zn4B 6 O 13 | 3％ | 109 | 80.8 |
| Example 16 | T a O 2 F | 3％ | 111 | 81.7 |
| Example 17 | Z r M g Mo 3 O 12 | 3％ | 108 | 80.5 |
| Example 18 | CaMn 7 O 12 | 3％ | 107 | 78.9 |
| Example 19 | Fe[Co(CN) 6 ] | 3％ | 112 | 79.1 |
| Example 20 | N(CH 3 ) 4 CuZn(CN) 4 | 3％ | 112 | 78.3 |
| Example 21 | T a O 2 F | 1％ | 114 | 81.7 |
| Example 22 | T a O 2 F | 5％ | 109 | 81.7 |
| Example 23 | ZrMgMo 3 O 12 | 1％ | 110 | 79.1 |
| Example 24 | ZrMgMo 3 O 12 | 5％ | 107 | 81.0 |
| Example 25 | Fe[Co(CN) 6 ] | 1％ | 112 | 77.7 |
| Example 26 | Fe[Co(CN) 6 ] | 5％ | 111 | 80.2 |
| Comparative example 4 | Al 2 O 3 | 3％ | 115 | 69.4 |
Note: the sintering temperature is 800 ℃, the sintering atmosphere is inert gas, and the sintering time is 24h.
As can be seen from the experimental results of comparative example 4 and examples 16 to 26, the coating of the positive electrode material with a material having a coefficient of thermal expansion close to zero improves the electrochemical properties of the lithium manganate material, also due to the thermal expansion coefficient (-1 x 10) of the coating material in the temperature range of use -6 ～3.5*10 -6 K -1 ) (in contrast to conventional coating materials: (>8*10 -6 K -1 ) The contact interface between the anode material and the electrolyte can be well stabilized, and the dissolution of manganese ions in the lithium manganate material can be inhibited.
In addition, fig. 1 shows a scanning electron microscope image (SEM) of the positive electrode material in example 9 as an example. FIG. 2 shows LiMnO 2 And the coated LiMnO of example 9 2 Cycle profile of the prepared lithium ion secondary battery. As can be seen from FIG. 2, zn 4 B 6 O 13 Coated LiMnO 2 The cycle capacity retention of the prepared lithium ion secondary battery is obviously high.
Those skilled in the art will appreciate that the above embodiments are only exemplary embodiments and that various changes, substitutions, and alterations can be made without departing from the spirit and scope of the application.
Claims (8)
1. A positive electrode material comprising:
a base material; and
a coating material formed on at least a part of a surface of the base material;
the coating material has a coefficient of thermal expansion of-4 x 10 at a temperature of 100K-400K -6 K -1 ～4*10 -6 K -1 ，
Wherein the coating material comprises TaO 2 F、ZrMgMo 3 O 12 、CaMn 7 O 12 、Fe[Co(CN) 6 ]And N (CH) 3 ) 4 CuZn(CN) 4 At least one of (1).
2. The positive electrode material according to claim 1, wherein the mass of the coating material accounts for 0.05 to 10% of the total mass of the base material and the coating material.
3. The positive electrode material according to claim 1, wherein the base material comprises at least one of the following materials:
LiMn 2 O 4 ；
Li(Ni x Co y Mn z )O 2 wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z =1;
LiMn 2-a O 4 M a wherein M is at least one of Li, mg, zr, al, ti, C and La, 0<a<2；
Li(Ni b Co c Mn d )O 2 N e Wherein, N is at least one of Mg, zr, al, ti, ce and La, and b + c + d + e =1.
4. A method of making a positive electrode material, comprising:
adding a coating material into a base material, and grinding and mixing to obtain a mixed material;
sintering the mixed material to obtain the anode material;
wherein the coating material has a coefficient of thermal expansion of-4 x 10 at a temperature of 100K to 400K -6 K -1 ～4*10 -6 K -1 ，
Wherein the coating material comprises TaO 2 F、Zn 4 B 6 O 13 、ZrMgMo 3 O 12 、CaMn 7 O 12 、Fe[Co(CN) 6 ]And N (CH) 3 ) 4 CuZn(CN) 4 At least one of (a).
5. The method of claim 4, wherein the temperature of the sintering is 400 ℃ to 900 ℃, the sintering is performed under an inert atmosphere, and the time of the sintering is 15 to 30 hours.
6. The method according to claim 4, wherein the proportion of the mass of the coating material to the total mass of the base material and the coating material is 0.05-10%.
7. A positive electrode sheet comprising:
a positive current collector; and
a positive electrode material disposed on the positive electrode current collector;
wherein the positive electrode material comprises the positive electrode material according to any one of claims 1 to 3 or the positive electrode material prepared by the method according to any one of claims 4 to 6.
8. A lithium ion secondary battery comprising the positive electrode sheet according to claim 7.
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