CN115732675A - Lithium ion battery anode material and preparation method thereof, lithium ion battery and electronic equipment - Google Patents
Lithium ion battery anode material and preparation method thereof, lithium ion battery and electronic equipment Download PDFInfo
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Abstract
The application discloses a positive electrode material of a lithium ion battery, a preparation method of the positive electrode material, the lithium ion battery and electronic equipment. In addition, because lithium ions in the cation disordered material are subjected to deintercalation under the action of high voltage, the cation disordered material can also provide more active lithium ions, so that the gram capacity of the cathode material is improved. When the cation disordered material generates larger impedance and polarization effects after multiple cycles, the fast ion conductor material can improve the impedance polarization effect and ensure the ion conductivity of the anode material.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a lithium ion battery anode material and a preparation method thereof.
Background
Fig. 1 is a schematic diagram of an exemplary lithium ion battery configuration. It can be seen that the lithium ion battery comprises a positive electrode, a negative electrode, an electrolyte, a diaphragm, a corresponding loop and the like. The positive/negative electrode material can release lithium ions to realize energy storage and release, the electrolyte is a carrier for lithium ions to be transmitted between the positive/negative electrodes, and the non-conductive diaphragm can be permeable to the lithium ions and separates the positive/negative electrodes to prevent short circuit. In the system, the positive electrode material is used as a supply source of lithium ions, and the capacity of the positive electrode material directly determines the energy density of the system.
The energy density of the traditional anode materials, such as lithium cobaltate, lithium iron phosphate, ternary materials and the like, can gradually fail to meet the requirements of new electronic equipment on the energy density of batteries. For the positive electrode material, by increasing its charge cut-off voltage and/or gram capacity, the discharge capacity and discharge voltage can be increased, thereby increasing the energy density of the battery. However, due to the structural instability of the conventional positive electrode material, the problems of serious oxygen evolution, side reaction at an electrolyte interface and the like caused by the increase of the charge cut-off voltage of the conventional positive electrode material are caused, and finally, the problems of poor cycle performance, poor high-temperature storage performance, poor safety performance and the like are caused.
Disclosure of Invention
The application provides a lithium ion battery anode material, a preparation method thereof, a lithium ion battery and electronic equipment, and aims to solve the problem that the performance of the lithium ion battery is poor due to the problems of oxygen evolution, electrolyte interface side reaction and the like in a high-voltage working scene of the traditional anode material.
In a first aspect, the present application provides a lithium ion battery positive electrode material, which includes a positive electrode material substrate, a cation disordered material layer coated on the surface of the positive electrode material substrate, and a fast ion conductor material layer; the cationic disordered material has the general formula:
Li 1+x MeO y F z
wherein x is more than or equal to 0.1 and less than or equal to 1, z is more than or equal to 0, me is at least one of Ni, co, mn, al, ti, V, cr, mn, fe, cu, zn, zr, nb, mo, ru, sn, sb and La.
The lithium ion battery anode material provided by the embodiment of the application can inhibit oxygen evolution of the anode material matrix by means of the stable oxygen lattice framework and compact structure of the cation disordered material, and isolate the anode material matrix from the electrolyte, so that the side reaction caused by contact of oxygen and the electrolyte is relieved. In addition, under the action of high voltage, lithium ions in the cation disordered material are subjected to deintercalation, so that the cation disordered material can provide more active lithium ions, and the gram capacity of the cathode material is improved. When the cation disordered material generates larger impedance and polarization effect after multiple cycles, the fast ion conductor material can improve the impedance polarization effect and ensure the ion conductivity of the anode material.
In an alternative implementation of the first aspect, the cation disordered material is Li 1.211 Mo 0.467 Cr 0.3 O 2 ，Li 2 Mn 2/ 3 Nb 1/3 O 2 F，Li 2 Mn 1/2 Ti 1/2 O 2 F，Li 1.68 Mn 1.6 O 3.7 F 0.3 ，Li 1.68 Mn 1.6 O 3.4 F 0.6 At least one of (1).
In an alternative implementation of the first aspect, the fast ion conductor material is an oxide-type solid electrolyte or a sulfide-type solid electrolyte. The oxide type solid electrolyte or the sulfide type solid electrolyte can improve the impedance polarization effect to ensure the ionic conductivity of the anode material, can still maintain stable physical and chemical properties under the action of high voltage, and is not easy to decompose.
In an alternative implementation of the first aspect, the sum of the mass of the cation disordered material and the mass of the fast ion conductor material accounts for 0.1-20% of the total mass of the cathode material.
In an alternative implementation of the first aspect, the mass ratio of the cation disordered material to the matrix of the cathode material is between 0.01 and 0.2. The appropriate coating amount of the cation disordered material can effectively inhibit oxygen evolution and avoid the influence of low lithium ion transmission rate on the capacity and rate performance of the battery.
In an alternative implementation of the first aspect, the mass ratio of the fast ion conductor material to the matrix of the positive electrode material is between 0.03 and 0.05. The proper coating amount of the fast ion conductor material can improve the impedance polarization effect without influencing the battery capacity.
In an optional implementation manner of the first aspect, the positive electrode material further includes a carbon material layer coated on the outermost side, and the carbon material layer can improve the electronic conductivity of the positive electrode material, and further reduce the impedance.
In an alternative implementation manner of the first aspect, the mass ratio of the carbon material layer to the positive electrode material substrate is less than or equal to 5%.
In an alternative implementation manner of the first aspect, the carbon material is one or more of carbon nanotube, carbon fiber, graphene, activated carbon, porous carbon, and graphite.
In an alternative implementation of the first aspect, the positive electrode material matrix has the general formula:
Li 1+c Co 1-a-b M a Al b O 2
wherein c is more than or equal to 0.05 and less than or equal to 0.3, a is more than or equal to 0 and less than or equal to 0.1, b is more than or equal to 0.02, and M is one or more of doping elements Mg, ti, mo, ni, mn, nb, W, cr and La.
In an alternative implementation of the first aspect, the cation disordered material is a lamellar phase, a spinel phase, or a rock salt phase.
In a second aspect, an embodiment of the present application provides a method for preparing a positive electrode material of a lithium ion battery, where the method mainly includes: uniformly mixing the precursor of the positive electrode material with a lithium source according to a preset molar ratio, and sintering at 800-1100 ℃ for 8-20h; crushing the sintered product to obtain a positive electrode material substrate; uniformly mixing a cation disordered material, a fast ion conductor material and a positive electrode material matrix according to a preset molar ratio, and sintering at 300-800 ℃ for 6-12h; crushing the sintered product to obtain a positive electrode material coated with a cation disordered material and a fast ion conductor material; wherein the cation disordered material has the general formula:
Li 1+x MeO y F z
wherein x is more than or equal to 0.1 and less than or equal to 1, z is more than or equal to 0, me is at least one of Ni, co, mn, al, ti, V, cr, mn, fe, cu, zn, zr, nb, mo, ru, sn, sb and La.
The positive electrode material coated by the cation disordered material and the fast ion conductor material can inhibit oxygen evolution of the positive electrode material matrix by means of the stable oxygen lattice framework and compact structure of the cation disordered material, and isolate the positive electrode material matrix from the electrolyte, so that side reaction caused by contact of oxygen and the electrolyte is relieved. And, the cation disordered material can also provide more active lithium ions, thereby improving the gram capacity of the cathode material. When the cation disordered material generates larger impedance and polarization effect after multiple cycles, the fast ion conductor material layer can improve the impedance polarization effect and ensure the ion conductivity of the anode material.
In an optional implementation manner of the second aspect, the positive electrode material precursor is one or more of cobaltosic oxide, cobalt carbonate, cobalt hydroxide, cobalt oxyhydroxide and ternary nickel-cobalt-manganese hydroxide doped with an M element and an Al element, and M is one or more of Mg, ti, mo, ni, mn, nb, W, cr and La.
In an optional implementation manner of the second aspect, the method may further include: after the positive electrode material coated with the cation disordered material and the fast ion conductor material and the carbon material are uniformly mixed according to the preset mass ratio, the positive electrode material coated with the cation disordered material, the fast ion conductor material and the carbon material is obtained through ball milling for 4-20 hours, and therefore the electronic conductivity of the positive electrode material is improved through coating the carbon material on the outermost layer, and the impedance is further reduced.
In an alternative implementation of the second aspect, the lithium source comprises one or more of lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate, lithium acetate, lithium oxide, lithium citrate.
In a third aspect, an embodiment of the present application further provides a lithium ion battery, which includes a positive electrode material, an electrolyte, a separator, and a negative electrode material, where the positive electrode material is the positive electrode material provided in the first aspect and coated with a cation disordered material and a fast ion conductor material. The positive electrode material has the performances of inhibiting oxygen evolution and relieving interface side reaction, so that the positive electrode material has higher charge cut-off voltage and energy density, and the cycle performance, the high-temperature storage performance, the safety performance and the like of the positive electrode material are not influenced by the improvement of the charge cut-off voltage.
In a fourth aspect, an embodiment of the present application further provides an electronic device, which includes a charging and discharging circuit and an electric element, and further includes the lithium ion battery provided in the third aspect of the present application, where the lithium ion battery is connected to the charging and discharging circuit, and is charged through the charging and discharging circuit or supplies power to the electric element.
Drawings
In order to more clearly explain the technical solution of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without any creative effort.
Fig. 1 is a schematic diagram of an exemplary lithium ion battery of the present application;
FIG. 2 is a schematic illustration of a particle structure of a positive electrode material shown in some embodiments herein;
FIG. 3 is a schematic illustration of the particle structure of the positive electrode material shown in other embodiments of the present application;
FIG. 4 is a schematic illustration of the particle structure of the positive electrode material shown in other embodiments of the present application;
FIG. 5 is a schematic illustration of the particle structure of the positive electrode material shown in other embodiments of the present application;
fig. 6 is a flow chart of a method of making a lithium-ion battery positive electrode material shown herein in some embodiments;
fig. 7 shows the results of the capacity retention rate test of the button cells according to examples 1, 2 and 1.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The embodiment of the application provides a positive electrode material coated with a cation disordered material and a fast ion conductor material, a lithium ion battery using the positive electrode material and electronic equipment using the lithium ion battery. The positive electrode material can inhibit oxygen evolution of a positive electrode material matrix by means of a stable oxygen lattice framework and a compact structure of a cation disordered material, and isolate the positive electrode material matrix from an electrolyte, so that side reactions caused by contact of oxygen and the electrolyte are relieved. Furthermore, the cation disordered material can provide more active lithium ions, so that the gram capacity of the cathode material is improved. When the cation disordered material generates larger impedance and polarization effect after multiple cycles, the fast ion conductor material layer can improve the impedance polarization effect and ensure the ion conductivity of the anode material. Wherein the cation disordered material has the general formula:
Li 1+x MeO y F z
wherein x is more than or equal to 0.1 and less than or equal to 1, z is more than or equal to 0, and satisfies the valence of 1+ x + A =2y + z, A is Me. Me is at least one of Ni, co, mn, al, ti, V, cr, mn, fe, cu, zn, zr, nb, mo, ru, sn, sb and La.
In some embodiments, the positive electrode material comprises a positive electrode material matrix, a cation disordered material layer coated outside the positive electrode material matrix, and a fast ion conductor material layer.
In some possible implementation manners, the cation disordered material layer is coated on the outer side surface of the cathode material base body, and the fast ion conductor material layer is coated on the outer side surface of the cation disordered material layer.
Fig. 2 is a schematic structural diagram of a positive electrode material particle shown in some embodiments of the present application, and as shown in fig. 2, the positive electrode material particle 200 includes a positive electrode material matrix 201, a cation disordered material layer 202, and a fast ion conductor material layer 203, wherein the cation disordered material layer 202 is coated on an outer surface of the positive electrode material matrix 201, and the fast ion conductor material layer 203 is coated on an outer side surface of the cation disordered material layer 202. Under the action of high voltage, on one hand, oxygen release on the surface of the cathode material substrate 201 can be inhibited based on the coating action of the cation disordered material layer 202, and on the other hand, contact between oxygen and electrolyte can be relieved based on the isolation action of the cation disordered material layer 202 and the fast ion conductor material layer 203 on the electrolyte, so that side reaction on the interface of the cathode material and the electrolyte is reduced, and feasibility is further provided for improving the charge cut-off voltage of the battery. It is noted that, compared with the coating layer made of other materials, the cation disordered material layer 202 not only can maintain a stable oxygen lattice framework and a compact structure under the action of high voltage, but also can provide more active lithium ions, so that the gram capacity of the cathode material is further improved on the basis of improving the charge cut-off voltage of the cathode material to improve the energy density of the battery. In addition, the fast ion conductor material layer 203 is further coated on the outer side of the cation disordered material layer 202, so that when the cation disordered material generates a large impedance and polarization effect after multiple cycles, the impedance polarization effect can be improved through the fast ion conductor material layer, and the ion conductivity of the anode material can be ensured.
In other possible implementations, the cation disordered material layer and the fast ion conductor material layer are a mixed clad layer composed of a cation disordered material and a fast ion conductor material.
Fig. 3 is a schematic structural diagram of a positive electrode material particle shown in some embodiments of the present application, and as shown in fig. 3, the positive electrode material particle 300 includes a positive electrode material matrix 301 and a mixed coating layer 302, wherein the mixed coating layer 302 is coated on an outer surface of the positive electrode material matrix 301. The mixed clad layer 302 is composed of a cation disordered material and a fast ion conductor material. Under the action of high voltage, on one hand, oxygen release on the surface of the anode material substrate 301 can be inhibited based on the coating action of the mixed coating layer 302, and on the other hand, contact between oxygen and electrolyte can be relieved based on the isolation action of the mixed coating layer 302 on the electrolyte, so that side reaction of an interface of the anode material and the electrolyte is reduced, and feasibility is provided for improving the charge cut-off voltage of the battery. It is worth noting that compared with the coating layer made of other materials, the cation disordered material not only can keep a stable oxygen lattice framework and a compact structure under the action of high voltage, but also can provide more active lithium ions, so that the gram capacity of the cathode material is further improved on the basis of improving the charge cut-off voltage of the cathode material to improve the energy density of the battery. In addition, the fast ion conductor material can improve the impedance polarization effect and ensure the ion conductivity of the anode material when the cation disordered material generates larger impedance and polarization effect after multiple cycles.
In certain embodiments, the positive electrode material matrix has the general formula:
Li 1+c Co 1-a-b M a Al b O 2
wherein c is more than or equal to 0.05 and less than or equal to 0.3, a is more than or equal to 0 and less than or equal to 0.1, b is more than or equal to 0.02, and M is one or more of doping elements Mg, ti, mo, ni, mn, nb, W, cr and La.
In certain embodiments, the cation disordered material is a lamellar phase, a spinel phase, or a rock salt phase.
In certain embodiments, the fast ion conductor material is an oxide-type solid electrolyte or a sulfide-type solid electrolyte. The oxide type solid electrolyte or the sulfide type solid electrolyte can improve the impedance polarization effect to ensure the ionic conductivity of the anode material, can still maintain stable physical and chemical properties under the action of high voltage, and is not easy to decompose.
Among them, oxide solid electrolytes can be classified into crystalline and glassy (amorphous) states according to the structure of the substance. The crystalline electrolyte includes perovskite type, NASICON type, LISICON type, garnet type, and the like. The oxide crystalline solid electrolyte has high chemical stability, can stably exist in atmospheric environment, and is beneficial to the large-scale production of all-solid batteries. The sulfide solid electrolyte is derived from oxide solid electrolyte, and oxygen in an oxide organism is replaced by sulfur to form the sulfide solid electrolyte. Sulfide solid electrolyte thio-LISICON type, glassy PS, siS, BS, liS, etc.
In certain embodiments, the sum of the mass of the cation disordered material and the fast ion conductor material layer is 0.1% -20% of the total mass of the positive electrode material. In other words, the mass ratio of the cation disordered material to the fast ion conductor material layer and to the positive electrode material matrix is between 0.1. In certain embodiments, the mass ratio of the cation disordered material to the positive electrode material matrix is between 0.01 and 0.2. In certain embodiments, the mass ratio of the layer of fast ion conductor material to the matrix of positive electrode material is between 0.03 and 0.05. The appropriate coating amount of the cation disordered material can effectively inhibit oxygen evolution and avoid the influence of low lithium ion transmission rate on the capacity and rate performance of the battery. The coating amount of the fast ion conductor material layer is suitable, so that the impedance polarization effect can be improved, and meanwhile, the battery capacity is not influenced.
In some embodiments, the lithium ion battery positive electrode material provided by the embodiments of the present application further includes a carbon material layer coated on the outermost side, where the carbon material layer can improve the electron conductivity of the positive electrode material, and further reduce the impedance. In some embodiments, the mass ratio of the carbon material layer to the matrix of the positive electrode material is 5% or less.
Fig. 4 is a schematic structural diagram of the cathode material particles shown in some embodiments of the present application, and as shown in fig. 4, the cathode material particles 400 include a cathode material matrix 401, a cation disordered material layer 402, a fast ion conductor material 403, and a carbon material layer 404. The cation disordered material layer 402 is coated on the outer surface of the cathode material substrate 401, the fast ion conductor material layer 403 is coated on the outer side surface of the cation disordered material layer 402, and the carbon material layer 404 is coated on the outer side surface of the fast ion conductor material layer 403.
Fig. 5 is a schematic structural diagram of the positive electrode material particles shown in some embodiments of the present application, and as shown in fig. 5, the positive electrode material particles 500 include a positive electrode material matrix 501, a mixed coating layer 502, and a carbon material layer 503. The mixed coating layer 502 is coated on the outer surface of the positive electrode material substrate 501, and the carbon material layer 503 is coated on the outer surface of the mixed coating layer 502. The mixed clad layer 502 is composed of a cation disordered material and a fast ion conductor material.
In certain embodiments, the carbon material is one or more of carbon nanotubes, carbon fibers, graphene, activated carbon, porous carbon, graphite.
The embodiment of the application also provides a preparation method of the lithium ion battery anode material. Fig. 6 is a flowchart of a method for preparing the lithium ion battery cathode material, and as shown in fig. 6, the method may include:
s601, uniformly mixing the precursor of the positive electrode material and a lithium source according to a preset molar ratio, and sintering at 800-1100 ℃ for 8-20h; and crushing the sintered product to obtain the anode material substrate.
In some embodiments, the positive electrode material precursor is one or more of cobaltosic oxide, cobalt carbonate, cobalt hydroxide, cobalt oxyhydroxide and ternary nickel-cobalt-manganese hydroxide doped with M element and Al element, and M is one or more of Mg, ti, mo, ni, mn, nb, W, cr and La.
In certain embodiments, the lithium source comprises one or more of lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate, lithium acetate, lithium oxide, lithium citrate.
It should be understood that the above listed positive electrode material precursors and lithium sources are only exemplary examples, and may also include other materials, which are not limited in the embodiments of the present application.
It should be noted that the crushed particle size of the sintered product obtained in S601 is not limited in the present application, and those skilled in the art can control the particle size of the cathode material substrate according to the design parameters of the battery in practical applications, and all of them fall within the scope of the present application.
In other embodiments, the sintering temperature in S601 can be controlled to be 1000-1050 ℃, and the sintering time can be controlled to be 10-18h.
S602, uniformly mixing the cation disordered material, the fast ion conductor material and the positive electrode material matrix according to a preset molar ratio, and sintering at 300-800 ℃ for 6-12h.
In the examples of the present application, the cation disordered material has the general formula:
Li 1+x MeO y F z
wherein x is more than or equal to 0.1 and less than or equal to 1, z is more than or equal to 0, me is at least one of Ni, co, mn, al, ti, V, cr, mn, fe, cu, zn, zr, nb, mo, ru, sn, sb and La.
Illustratively, the cationic disordered material is Li 1.211 Mo 0.467 Cr 0.3 O 2 ，Li 2 Mn 2/3 Nb 1/3 O 2 F，Li 2 Mn 1/2 Ti 1/ 2 O 2 F，Li 1.68 Mn 1.6 O 3.7 F 0.3 ，Li 1.68 Mn 1.6 O 3.4 F 0.6 At least one of (1).
Illustratively, the fast ion conductor may be Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Or a lithium ion conductive ceramic powder with model number LATP purchased from shenzhenjian crystal zhida technology ltd.
It should be understood that the cation disordered material and the fast ion conductor material listed above are only exemplary examples, and may also include other materials, which are not limited by the embodiments of the present application.
In certain embodiments, the sum of the mass of the layer of cation disordered material and the layer of fast ion conductor material is 0.1% to 20% of the total mass of the positive electrode material. The mass ratio of the cation disordered material to the positive electrode material matrix is 0.01-0.2. The mass ratio of the fast ion conductor material layer to the positive electrode material substrate is between 0.03 and 0.05. In these embodiments, the mixing ratio between the cation disordered material, the fast ion conductor material, and the positive electrode material matrix can be determined accordingly.
And S603, crushing the sintered product obtained in the step S602 to obtain the positive electrode material coated with the cation disordered material and the fast ion conductor material.
In some embodiments, the method for preparing a positive electrode material of a lithium ion battery provided in the embodiments of the present application further includes:
s604, uniformly mixing the positive electrode material coated with the cation disordered material and the fast ion conductor material with the carbon material according to a preset mass ratio, and performing ball milling treatment for 4-20h at a rotating speed of 350r/min to obtain the positive electrode material coated with the cation disordered material, the fast ion conductor material and the carbon material.
In addition, the present application does not limit the crushed particle size of the sintered product obtained in S603, the ball-to-material ratio used in S604, and the target particle size, and those skilled in the art can control the particle size of the cathode material according to the design parameters of the battery in practical application, and all of them fall within the protection scope of the present application.
It should be noted that by adjusting the above steps for preparing the cathode material, cathode material particles having the structure shown in fig. 2 can be obtained. For example, after a positive electrode material matrix is prepared, a cation disordered material and the positive electrode material matrix are uniformly mixed according to a preset molar ratio, then sintered and crushed to obtain a positive electrode material intermediate only coated with the cation disordered material, wherein the positive electrode material intermediate is composed of the positive electrode material matrix and a cation disordered material layer coated on the outer side; then, the positive electrode material intermediate and the fast ion conductor material are uniformly mixed according to a preset molar ratio, and then sintered and crushed to obtain positive electrode material particles sequentially coated by the cation disordered material and the fast ion conductor material, wherein the structure of the positive electrode material particles can be shown in fig. 2, and is not repeated here.
The following describes the preparation method of the above-mentioned cathode material by specific examples, and a lithium ion battery is prepared by using the cathode material sample prepared in the examples, and the capacity retention rate of the lithium ion battery under a higher charge cut-off voltage is tested.
Example 1
S101, mixing Co with the Al molar content of 1%, the Mg molar content of 0.5% and the Ti molar content of 0.2% 3 O 4 The precursor and lithium carbonate are evenly mixed according to the mol ratio of Li to Co =1.05, and then are placed in a muffle furnaceSintering at 1050 ℃ for 12h. After sintering, cooling to room temperature according to a preset cooling rate, and crushing a sintered product to obtain a lithium cobaltate matrix material LiCo 0.983 Al 0.01 Mg 0.005 Ti 0.002 O 2 。
S102, preparing a lithium cobaltate base material and a cation disordered material Li 2 Mn 2/3 Nb 1/3 O 2 F. Fast ion conductor material Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Uniformly mixing according to the molar ratio of 100.
And S103, crushing the sintered product in the S102 to obtain the lithium cobaltate positive electrode material which is coated by the cation disordered material and the fast ion conductor material.
S104, mixing the lithium cobaltate positive electrode material co-coated with the cation disordered material and the fast ion conductor material with the graphene powder material according to the mass ratio of 100.5, and performing ball milling for 4-20 hours at the rotating speed of 350r/min to obtain the lithium cobaltate positive electrode material co-coated with the cation disordered material, the fast ion conductor and the carbon material.
Example 2
S201, mixing Co with the Al molar content of 1%, the Mg molar content of 0.5% and the Ti molar content of 0.2% 3 O 4 The precursor and lithium carbonate are uniformly mixed according to the molar ratio of Li to Co =1.05, and then are placed in a muffle furnace to be sintered for 12 hours at 1050 ℃. After sintering, cooling to room temperature according to a preset cooling rate, and crushing a sintered product to obtain a lithium cobaltate matrix material LiCo 0.983 Al 0.01 Mg 0.005 Ti 0.002 O 2 。
S202, preparing a lithium cobaltate base material and a fast ion conductor material Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Uniformly mixing according to the molar ratio of 100. And after sintering, crushing the sintered product to obtain the lithium cobaltate positive electrode material coated with the fast ion conductor material.
S203, using the cation disordered positive electrode of the material obtained in the S202Material Li 2 Mn 2/3 Nb 1/3 O 2 And F is uniformly mixed according to the molar ratio of 100 to 0.3, and then is placed in a muffle furnace to be sintered for 8 hours at 400 ℃. And after sintering, crushing the sintered product to obtain the lithium cobaltate cathode material which is coated by the cation disordered material and the fast ion conductor material.
Comparative example 1
Firstly, co with the Al-doped mol content of 1%, the Mg-doped mol content of 0.5% and the Ti-doped mol content of 0.2% is added 3 O 4 The precursor and lithium carbonate are uniformly mixed according to the molar ratio of Li to Co =1.05, and then are placed in a muffle furnace to be sintered for 12 hours at 1050 ℃. After sintering, cooling to room temperature according to a preset cooling rate, and crushing a sintered product to obtain a lithium cobaltate matrix material LiCo 0.983 Al 0.01 Mg 0.005 Ti 0.002 O 2 。
Then, the lithium cobaltate base material and Al are mixed 2 O 3 The nano powder is uniformly mixed according to the proportion of 100. After sintering, crushing the sintered product to obtain Al 2 O 3 A coated lithium cobaltate cathode material.
The positive electrode materials obtained in example 1, example 2, and comparative example 1 were dispersed in an N-methylpyrrolidone (NMP) solvent, together with a conductive agent carbon black and a binder polyvinylidene fluoride (PVDF), at a mass ratio of 95. And coating the positive electrode slurry on the surface of an aluminum foil, and drying at 120 ℃ to obtain the positive electrode piece. And matching the positive pole piece with a lithium metal negative pole to manufacture the button type lithium ion battery. Wherein the electrolyte adopted is 1mol/L LiPF 6 The separator used was a PP/PE/PP trilayer separator with a separator thickness of 16um (EC + PC + DEC + EMC (volume ratio 1. The capacity retention rates of the button cells corresponding to examples 1, 2 and 1 are shown in fig. 7 under the condition that the charge cut-off voltage is 3-4.6V.
As shown in fig. 7, the capacity retention rate of the button lithium ion battery corresponding to comparative example 1 rapidly decreased with the increase of the number of cycles, which was much lower than those of examples 1 and 2. The control lithium ion batteries corresponding to the embodiments 1 and 2 can still maintain better capacity under the working condition of higher charge cut-off voltage. Therefore, the lithium ion battery prepared by the cathode material provided by the embodiment of the application still has good cycle performance and capacity retention rate under high charge cut-off voltage, and the performance of the lithium ion battery is not influenced by the improvement of the charge cut-off voltage.
Based on the lithium ion battery that above-mentioned embodiment provided, this application embodiment still provides an electronic equipment, including charge and discharge circuit and with the electric element, still include the lithium ion battery that this application provided, this lithium ion battery is connected with charge and discharge circuit, charges or for supplying power with the electric element through charge and discharge circuit.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention.
Claims (17)
1. The positive electrode material of the lithium ion battery is characterized by comprising a positive electrode material matrix, a cation disordered material layer and a fast ion conductor material layer, wherein the cation disordered material layer and the fast ion conductor material layer are coated on the outer side of the positive electrode material matrix; the cation disordered material has the general formula:
Li 1+x MeO y F z
wherein x is more than or equal to 0.1 and less than or equal to 1, z is more than or equal to 0, me is at least one of Ni, co, mn, al, ti, V, cr, mn, fe, cu, zn, zr, nb, mo, ru, sn, sb and La.
2. The lithium ion battery positive electrode material according to claim 1, wherein the cation-disordered material is Li 1.211 Mo 0.467 Cr 0.3 O 2 ，Li 2 Mn 2/3 Nb 1/3 O 2 F，Li 2 Mn 1/2 Ti 1/2 O 2 F，Li 1.68 Mn 1.6 O 3.7 F 0.3 ，Li 1.68 Mn 1.6 O 3.4 F 0.6 At least one of (1).
3. The lithium ion battery cathode material according to claim 1, wherein the fast ion conductor material is an oxide-type solid electrolyte or a sulfide-type solid electrolyte.
4. The positive electrode material of the lithium ion battery according to claim 1, wherein the sum of the mass of the cation disordered material and the mass of the fast ion conductor material accounts for 0.1-20% of the total mass of the positive electrode material.
5. The lithium ion battery cathode material according to claim 4, wherein the mass ratio of the cation disordered material to the cathode material matrix is between 0.01 and 0.2.
6. The positive electrode material of claim 4, wherein the mass ratio of the fast ion conductor material to the positive electrode material matrix is between 0.03 and 0.05.
7. The lithium ion battery cathode material according to claim 1, further comprising a carbon material layer coated outside the cation disordered material layer and the fast ion conductor material layer.
8. The lithium ion battery cathode material according to claim 7, wherein the mass ratio of the carbon material layer to the cathode material matrix is less than or equal to 5%.
9. The lithium ion battery positive electrode material according to claim 7, wherein the carbon material is one or more of carbon nanotubes, carbon fibers, graphene, activated carbon, porous carbon, and graphite.
10. The positive electrode material for the lithium ion battery according to claim 1, wherein the positive electrode material matrix has a general formula:
Li 1+c Co 1-a-b M a Al b O 2
wherein c is more than or equal to 0.05 and less than or equal to 0.3, a is more than or equal to 0 and less than or equal to 0.1, b is more than or equal to 0.02, and M is one or more of doping elements Mg, ti, mo, ni, mn, nb, W, cr and La.
11. The lithium ion battery positive electrode material according to claim 1, wherein the cation disordered material is a lamellar phase, a spinel phase, or a rock salt phase.
12. A preparation method of a lithium ion battery positive electrode material is characterized by comprising the following steps:
uniformly mixing the precursor of the positive electrode material with a lithium source according to a preset molar ratio, and sintering at 800-1100 ℃ for 8-20h; crushing the sintered product to obtain a positive electrode material substrate;
uniformly mixing a cation disordered material, a fast ion conductor material and a positive electrode material matrix according to a preset molar ratio, and sintering at 300-800 ℃ for 6-12h; crushing the sintered product to obtain a positive electrode material coated with a cation disordered material and a fast ion conductor material;
wherein the cation disordered material has the general formula:
Li 1+x MeO y F z
wherein x is more than or equal to 0.1 and less than or equal to 1, z is more than or equal to 0, me is at least one of Ni, co, mn, al, ti, V, cr, mn, fe, cu, zn, zr, nb, mo, ru, sn, sb and La.
13. The method according to claim 12, wherein the precursor of the positive electrode material is one or more of cobaltosic oxide, cobalt carbonate, cobalt hydroxide, cobalt oxyhydroxide and ternary nickel cobalt manganese hydroxide doped with M element and Al element, and M is one or more of Mg, ti, mo, ni, mn, nb, W, cr and La.
14. The method of claim 12, further comprising:
uniformly mixing the positive electrode material coated with the cation disordered material and the fast ion conductor material with the carbon material according to a preset mass ratio, and performing ball milling treatment for 4-20h to obtain the positive electrode material coated with the cation disordered material, the fast ion conductor material and the carbon material.
15. The method of claim 12, wherein the lithium source comprises one or more of lithium hydroxide, lithium nitrate, lithium carbonate, lithium oxalate, lithium acetate, lithium oxide, lithium citrate.
16. A lithium ion battery comprises a positive electrode material, an electrolyte, a diaphragm and a negative electrode material, and is characterized in that the positive electrode material is the positive electrode material of the lithium ion battery in any one of claims 1 to 11.
17. An electronic device comprising a charging and discharging circuit and an electric element, further comprising the lithium ion battery of claim 16, wherein the lithium ion battery is connected to the charging and discharging circuit, and is charged by the charging and discharging circuit or supplies power to the electric element.
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