CN113161547A - Ternary positive electrode material coated with PTC material, preparation method of ternary positive electrode material, lithium ion battery positive electrode material and lithium ion battery - Google Patents
Ternary positive electrode material coated with PTC material, preparation method of ternary positive electrode material, lithium ion battery positive electrode material and lithium ion battery Download PDFInfo
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Abstract
The invention provides a ternary cathode material coated with a PTC material, a preparation method of the ternary cathode material, a lithium ion battery cathode material and a lithium ion battery, and relates to the technical field of lithium ion battery cathode materials. The invention selects sodium bismuth titanate as the main component for forming the PTC material layer to coat the surface of the ternary cathode material, so that the resistance of the PTC material layer is increased in a step-like manner along with the increase of the temperature, thereby reducing the current, inhibiting the occurrence of side reactions, and improving the high-temperature service life and the safety performance of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a ternary cathode material coated with a PTC material, a preparation method of the ternary cathode material, a lithium ion battery cathode material and a lithium ion battery.
Background
In recent years, the new energy industry and the development of modern society have higher and higher intelligent requirements, the requirements of fixed and movable power supplies are continuously increased, and the goods output of lithium ion batteries is gradually increased in recent years in the fields of power batteries and 3C. Currently, commercially available lithium ion positive electrode materials mainly include lithium cobaltate and a ternary positive electrode material having a layered structure, lithium manganate having a spinel structure, and lithium iron phosphate having an olivine structure. Compared with other anode materials, the ternary anode material has higher specific capacity, energy density and power density and more stable performance, so that the ternary anode material becomes a popular material of a commercial anode, and the ternary anode material is the most demanded anode material at present by virtue of the rapid development of power batteries and the requirement of the power batteries on high energy density.
Nevertheless, the electrochemical performance, thermal stability and structural stability of the ternary cathode material need to be further improved, and particularly under high-temperature and high-potential test environments, the problems are more obvious along with the increasing of the nickel content, so that the ternary cathode material is very important for modification. So far, the modification of the ternary cathode material mainly comprises the steps of improving the lithium ion conductivity and the electronic conductivity of the ternary cathode material by a doping means, and reducing or inhibiting the occurrence of side reactions, so that the structural stability, the thermal stability, the rate capability and the long cycle performance of the ternary cathode material are improved. However, the conductivity of the ternary cathode material is reduced at high temperature, lithium ions diffuse faster, the reaction activity is higher, side reactions are more severe, and the safety problem of the battery is still more severe.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
One of the objectives of the present invention is to provide a ternary cathode material coated with a PTC material, so as to alleviate the technical problem that the conventional doping method for modifying the ternary cathode material can only inhibit the reaction between the electrolyte and the surface of the ternary cathode material at low temperature, but cannot effectively improve the side reaction of the ternary cathode material at high temperature, which leads to severe safety problems of the battery at high temperature.
The ternary cathode material coated with the PTC material comprises the ternary cathode material, wherein the surface of the ternary cathode material is coated with a PTC material layer, and the PTC material layer is mainly formed by sodium bismuth titanate.
Further, the mass ratio of the sodium bismuth titanate to the ternary cathode material is (0.05-0.5): 100, preferably (0.1-0.2): 100.
further, the sodium bismuth titanate is prepared according to the following steps:
adding soluble bismuth salt, soluble titanium salt and NaOH into water, uniformly mixing, and carrying out hydrothermal reaction to obtain sodium bismuth titanate, wherein the molar ratio of the soluble bismuth salt to the soluble titanium salt is 1: 2.
Further, the temperature of the hydrothermal reaction is 140-;
preferably, the soluble bismuth salt comprises at least one of bismuth nitrate or bismuth chloride, preferably bismuth nitrate;
preferably, the soluble titanium salt comprises at least one of titanium nitrate or titanium chloride, preferably titanium chloride.
Further, the ternary positive electrode material comprises nickel cobalt lithium manganate;
preferably, the lithium nickel cobalt manganese oxide comprises LiNi0.3Co0.3Mn0.3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2Or LiNi0.8Co0.1Mn0.1O2At least one of (1).
The invention also provides a preparation method of the ternary cathode material coated with the PTC material, which comprises the following steps:
and uniformly mixing sodium bismuth titanate and the ternary cathode material, and sintering to ensure that the sodium bismuth titanate is uniformly coated on the surface of the ternary cathode material to form the PTC material layer.
Further, the sintering temperature is 300-;
preferably, the sintering temperature is 400-;
preferably, the rate of temperature increase from room temperature to the sintering temperature is 2.5-3.5 deg.C/min, preferably 3 deg.C/min, prior to sintering.
Further, the mass ratio of the sodium bismuth titanate to the ternary cathode material is (0.05-0.5): 100, preferably (0.2-0.4): 100.
the third purpose of the invention is to provide a lithium ion battery anode material, which comprises the ternary anode material coated with the PTC material provided by the first purpose of the invention or the ternary anode material coated with the PTC material prepared by the preparation method provided by the second purpose of the invention.
The fourth purpose of the invention is to provide a lithium ion battery, which comprises the ternary cathode material coated with the PTC material provided by the first purpose of the invention, the ternary cathode material coated with the PTC material prepared by the preparation method provided by the second purpose of the invention or the lithium ion battery cathode material provided by the third purpose of the invention.
The ternary cathode material coated with the PTC material provided by the invention at least has the following beneficial effects:
sodium bismuth titanate (Na)0.5Bi0.5TiO3) The invention relates to a semiconductor resistor with temperature sensitivity, wherein sodium bismuth titanate is selected as a main component for forming a PTC material layer and is coated on the surface of a ternary cathode material, so that the resistance of the PTC material layer is increased in a step mode along with the increase of the temperature, thereby reducing the current, inhibiting the occurrence of side reactions, and improving the high-temperature service life and the safety performance of a lithium ion battery.
According to the preparation method of the ternary cathode material coated with the PTC material, provided by the invention, the sodium bismuth titanate is coated on the surface of the ternary cathode material in a sintering manner to form the compact PTC material layer, so that the PTC material layer and the ternary cathode material are connected through sintering, and the compactness and stability are combined, so that the structural stability of the ternary cathode material coated with the PTC material is effectively improved, and the high-temperature service life and the safety performance of a lithium ion battery are more effectively improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a graph showing high-temperature cycle curves of pouch batteries provided in example 7 of the present invention and comparative example 4.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. 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 invention.
According to one aspect of the invention, the invention provides a ternary cathode material coated with a PTC material, which comprises a ternary cathode material, wherein the surface of the ternary cathode material is coated with a PTC material layer, and the PTC material layer is mainly formed by sodium bismuth titanate.
In the present invention, PTC is an abbreviation of Positive Temperature Coefficient, and generally refers to a semiconductor material having a large Positive Temperature Coefficient.
In the present invention, the molecular formula of sodium bismuth titanate is Na0.5Bi0.5TiO3。
The sodium bismuth titanate is a typical PTC material, has temperature sensitivity, and when the temperature exceeds a certain temperature (Curie temperature), the resistance value of the sodium bismuth titanate is increased in a step-like manner along with the increase of the temperature, so that when the temperature of the lithium ion battery is increased due to insufficient heat dissipation, excessive heat generation or thermal runaway, the resistance of the battery anode material is increased, the current is reduced, the occurrence of side reactions is inhibited, and the high-temperature service life and the safety performance of the battery are improved.
Preferably, in the ternary cathode material coated with the PTC material provided by the present invention, the mass ratio of the sodium bismuth titanate to the ternary cathode material is (0.05-0.5): 100 to increase the resistance at high temperature through the PTC material layer to block ion transmission, thereby ensuring the safety of the battery. Meanwhile, the problem that the transmission of lithium ions and electrons is influenced due to the fact that the formed PTC material layer is too thick due to the fact that the using amount of the sodium bismuth titanate is too large can be avoided.
Typically, but not by way of limitation, the mass ratio of the sodium bismuth titanate to the ternary positive electrode material is, for example, 0.05:100, 0.08:100, 0.1:100, 0.15:100, 0.2:100, 0.25:100, 0.3:100, 0.35:100, 0.4:100, 0.45:100, or 0.5: 100.
In the ternary cathode material coated with the PTC material, the mass ratio of the sodium bismuth titanate to the ternary cathode material is 0.1-0.2: at 100 hours, the prepared lithium ion battery has more beneficial safety performance, rate capability and long cycle stability.
In a preferred embodiment of the invention, the sodium bismuth titanate is prepared by the following steps:
adding soluble bismuth salt, soluble titanium salt and NaOH into water, uniformly mixing, and carrying out hydrothermal reaction to obtain the sodium bismuth titanate.
Wherein, NaOH is enough to promote the reaction.
In a preferred embodiment of the present invention, the molar ratio of the soluble bismuth salt to the soluble titanium salt is 1:2, to facilitate the formation of sodium bismuth titanate.
The molar ratio of the soluble bismuth salt to the soluble titanium salt means the molar ratio of bismuth atoms in the soluble bismuth salt to titanium atoms in the soluble titanium salt.
Preferably, the temperature for carrying out the hydrothermal reaction is 140-.
Typically, but not by way of limitation, the hydrothermal reaction is carried out at a temperature of, for example, 140, 145, 150, 155, 160, 165, 170, 175, or 180 ℃ and a hydrothermal hold time of, for example, 10, 11, 12, 13, 14, or 15 hours.
In a preferred embodiment of the present invention, the soluble bismuth salt is bismuth nitrate, bismuth chloride or a mixture of bismuth nitrate and bismuth chloride, and especially when the soluble bismuth salt is bismuth nitrate, the hydrothermal reaction is more favorable for preparing the bismuth sodium titanate.
In a preferable scheme of the invention, the soluble titanium salt is titanium nitrate, titanium chloride or a mixture of the titanium nitrate and the titanium chloride, and particularly when the soluble titanium salt is the titanium chloride, the hydrothermal reaction is more favorable for preparing the sodium bismuth titanate.
In a preferred scheme of the invention, the ternary cathode material is nickel cobalt lithium manganate so as to improve the electrochemical performance, thermal stability and structural stability of the lithium ion battery cathode material.
Preferably, the lithium nickel cobalt manganese oxide comprises LiNi0.3Co0.3Mn0.3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2Or LiNi0.8Co0.1Mn0.1O2Any one or at least two of them.
According to a second aspect of the present invention, there is provided a method for preparing the above ternary cathode material coated with a PTC material, comprising the steps of:
and uniformly mixing sodium bismuth titanate and the ternary cathode material, and sintering to ensure that the sodium bismuth titanate is uniformly coated on the surface of the ternary cathode material to form the PTC material layer.
According to the preparation method of the ternary cathode material coated with the PTC material, provided by the invention, the sodium bismuth titanate is coated on the surface of the ternary cathode material in a sintering manner to form the compact PTC material layer, so that the PTC material layer and the ternary cathode material are connected through sintering, and the compactness and stability are combined, so that the structural stability of the ternary cathode material coated with the PTC material is effectively improved, and the high-temperature service life and the safety performance of a lithium ion battery are more effectively improved.
In a preferred scheme of the invention, the sintering temperature is 300-700 ℃, and the heat preservation time is 5-7h, so that the sodium bismuth titanate is coated on the surface of the ternary cathode material to form a uniform and compact PTC material layer.
Typically, but not by way of limitation, the sintering temperature is, for example, 300, 400, 500, 600 or 700 ℃ and the holding time is, for example, 5, 5.5, 6, 6.5 or 7 hours.
Preferably, when the sintering temperature is 400-.
In a preferred scheme of the invention, after the sodium bismuth titanate and the ternary cathode material are mixed and before the sintering temperature is reached, the temperature rise rate from the room temperature to the sintering temperature is controlled to be 2.5-3.5 ℃/min, so that a uniform and compact PTC material layer can be generated, and particularly, when the temperature rise rate is 3 ℃/min, the performance of the generated PTC material layer is more excellent.
Typically, but not by way of limitation, the ramp rate from room temperature to the sintering temperature, prior to sintering, is, for example, 2.5, 2.8, 3, 3.2, or 3.5 deg.C/min.
In a preferable scheme of the invention, the mass ratio of the sodium bismuth titanate to the ternary cathode material is (0.05-0.5): 100, so as to avoid incompact PTC coating layer formed due to too little bismuth sodium titanate dosage, and also avoid too thick PTC material layer formed due to too much bismuth sodium titanate dosage, which affects the transmission of lithium ions and electrons, especially when the mass ratio of bismuth sodium titanate to ternary cathode material is 0.1-0.2: the performance of the ternary cathode material coated with the PTC material prepared at 100 hours is more excellent.
According to a third aspect of the invention, the invention provides a lithium ion battery cathode material, which comprises the ternary cathode material provided by the first aspect of the invention or the ternary cathode material coated with the PTC material prepared by the preparation method provided by the second aspect of the invention.
The lithium ion battery anode material provided by the invention can also comprise an adhesive, a conductive agent and the like, so that the battery safety performance is ensured, and meanwhile, the lithium ion battery anode material has excellent rate performance and long cycle performance.
According to a fourth aspect of the invention, the invention provides a lithium ion battery, which comprises the ternary cathode material provided by the first aspect of the invention, the ternary cathode material coated with the PTC material prepared by the preparation method provided by the second aspect of the invention, or the lithium ion battery cathode material provided by the third aspect of the invention.
According to the lithium ion battery provided by the invention, the ternary cathode material coated with the PTC material is used as the active material, so that the lithium ion conductivity and the electronic conductivity are improved, and meanwhile, the thermal stability, the rate capability and the long-cycle stability of the lithium ion battery can be obviously improved.
In order to facilitate understanding of those skilled in the art, the technical solutions provided by the present invention are further described below with reference to examples and comparative examples.
Example 1
The embodiment provides a ternary cathode material coated with a PTC material, which is prepared according to the following steps: 4g of sodium bismuth titanate and 3000g of LiNi are weighed respectively0.3Co0.3Mn0.3O2Placing the powder into a small high-speed mixer, stirring for 30min to uniformly disperse, placing the mixed powder into a muffle furnace in air atmosphere, heating to 400 ℃ at the heating rate of 3 ℃/min, roasting for 6h, and sieving the cooled powder through a 400-mesh screen to obtain the ternary cathode material coated with the PTC material, wherein the bismuth sodium titanate is prepared according to the following steps:
adding a portion of Bi (NO) according to molar ratio3)3·5H2O, 2 parts of TiCl4Adding sufficient NaOH into deionized water, magnetically stirring for 30min, pouring the solution into a reaction kettle after the NaOH is completely dissolved, and sealing and reinforcing. And (3) placing the reaction kettle in a muffle furnace, heating to a certain temperature of 160 ℃, and preserving the temperature for about 12 hours. Filtering the solution after the hydrothermal reaction, repeatedly washing impurities by deionized water, and heating and drying in the air. The dried powder is Na prepared by hydrothermal reaction0.5Bi0.5TiO3And (3) nano materials.
Example 2
The embodiment provides a ternary cathode material coated with a PTC material, which is prepared according to the following steps:
5g of sodium bismuth titanate and 3000g of LiNi are weighed respectively0.6Co0.2Mn0.2O2Placing into a small high-speed mixer, stirring for 30min to disperse uniformly, placing the mixed powder into a muffle furnace in air atmosphere, heating to 500 deg.C at a heating rate of 3 deg.C/min, roasting for 6h, cooling, sieving with 400 mesh sieve to obtain ternary cathode material coated with PTC material。
The sodium bismuth titanate used in this example was the same batch as the sodium bismuth titanate used in example 1.
Example 3
The embodiment provides a ternary cathode material coated with a PTC material, and the preparation method of the ternary cathode material is different from that of embodiment 1 in that the amount of bismuth titanate is 3g, and the rest steps are the same as those of embodiment 2, and are not described herein again.
Example 4
The embodiment provides a ternary cathode material coated with a PTC material, and the preparation method of the ternary cathode material is different from that of embodiment 1 in that the amount of bismuth titanate is 6g, and the rest steps are the same as those of embodiment 2, and are not described herein again.
Example 5
The embodiment provides a ternary cathode material coated with a PTC material, and the preparation method of the ternary cathode material is different from that of embodiment 1 in that the amount of bismuth titanate is 1.5g, and the rest steps are the same as those of embodiment 2, and are not repeated herein.
Example 6
The embodiment provides a ternary cathode material coated with a PTC material, and the preparation method of the ternary cathode material is different from that of embodiment 1 in that the amount of bismuth titanate is 15g, and the rest steps are the same as those of embodiment 2, and are not described herein again.
Example 7
The embodiment provides a ternary cathode material coated with a PTC material, which is prepared according to the following steps: 6g of sodium bismuth titanate and 3000g of LiNi are weighed respectively0.8Co0.1Mn0.1O2And (3) putting the mixture into a small high-speed mixer, stirring for 30min to uniformly disperse, placing the mixed powder into a muffle furnace in an air atmosphere, heating to 600 ℃ at the heating rate of 3 ℃/min, roasting for 6h, and sieving the cooled powder through a 400-mesh screen to obtain the ternary cathode material coated with the PTC material.
Comparative example 1
The comparative example provides a ternary cathode material coated with PTC material, and the preparation method is different from that of example 1 in that nano TiO is adopted2Powder instead of bismuth titanateA sodium nanomaterial.
Comparative example 2
The comparative example provides a ternary cathode material coated with PTC material, and the difference between the preparation method of the ternary cathode material and the embodiment 2 is that nano TiO is adopted2The powder replaces the sodium bismuth titanate nano material.
Comparative example 3
The comparative example provides a ternary cathode material coated with PTC material, and the difference between the preparation method of the ternary cathode material and the embodiment 3 is that nano TiO is adopted2The powder replaces the sodium bismuth titanate nano material.
Comparative example 4
The comparative example provides a ternary cathode material coated with PTC material, and the preparation method is different from that of example 7 in that nano TiO is adopted2The powder replaces the sodium bismuth titanate nano material.
Test example 1
The ternary positive electrode materials coated with the PTC materials provided in the above examples and comparative examples were respectively used to fabricate 2Ah pouch cells. The specific method comprises the following steps: adding the materials into an NMP solvent according to the mass ratio, and uniformly mixing to prepare slurry with the solid content of 65%, wherein the positive electrode material comprises 96.5% of Super P, KS-6 and PVDF, 2% of the Super P, 0.5% of the PVDF and 1%. The slurry was applied by a coater, and the areal density of the coating side was set to 18.5mg/cm2And rolled by a roll press, with the compaction density set at 3.5g/cm 3. The negative electrode was formed by coating a graphite slurry on a copper foil, and the separator was formed into a 2Ah pouch battery using celgard 2400 and 1M LiPF6 having EC: EMC: DEC: 4:2 as an electrolyte. The manufactured batteries are respectively subjected to high-temperature cycle tests (2.8V-4.3V, 1C/4C and 45 ℃), gas production storage tests (1C is fully charged with 4.3V and is stored at 85 ℃ for 24 hours), hotbox tests (the batteries are fully charged according to the 1C multiplying power and then are placed in a hot box, the temperature is increased from the normal temperature to (150 ℃ plus or minus 2 ℃) at the speed of (5 ℃ plus or minus 2 ℃) per minute and is kept for 30 minutes, and the explosion and ignition conditions of the batteries are observed. The results are shown in table 1 below.
TABLE 1
As can be seen from Table 1, the conductivity at high temperature can be effectively reduced by coating the surface of the ternary cathode material with the sodium bismuth titanate nanomaterial to form a coating layer. The internal short-circuit current is obviously reduced, so that the risk of thermal runaway inside the anode material is obviously reduced, and the cycle and storage performance of the lithium ion battery at high temperature are obviously improved.
Fig. 1 is a high-temperature cycle curve diagram of the pouch battery prepared in example 7 and comparative example 4, and it can be seen from fig. 1 that the battery prepared by using the ternary cathode material coated with the PTC material provided in example 7 is more excellent in high-temperature cycle performance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The ternary cathode material coated with the PTC material is characterized by comprising the ternary cathode material, wherein the surface of the ternary cathode material is coated with a PTC material layer, and the PTC material layer is mainly formed by sodium bismuth titanate.
2. The ternary positive electrode material coated with a PTC material according to claim 1, wherein the mass ratio of sodium bismuth titanate to the ternary positive electrode material is (0.05-0.5): 100, preferably (0.1-0.2): 100.
3. a PTC material-coated ternary positive electrode material according to claim 1, wherein the sodium bismuth titanate is prepared by the following steps:
adding soluble bismuth salt, soluble titanium salt and NaOH into water, uniformly mixing, and carrying out hydrothermal reaction to obtain bismuth sodium titanate;
preferably, the molar ratio of the soluble bismuth salt to the soluble titanium salt is 1: 2.
4. The ternary cathode material coated with the PTC material according to claim 3, wherein the temperature of the hydrothermal reaction is 140-180 ℃, and the hydrothermal heat preservation time is 10-15 h;
preferably, the soluble bismuth salt comprises at least one of bismuth nitrate or bismuth chloride, preferably bismuth nitrate;
preferably, the soluble titanium salt comprises at least one of titanium nitrate or titanium chloride, preferably titanium chloride.
5. A ternary positive electrode material coated with a PTC material according to any one of claims 1 to 4, wherein the ternary positive electrode material comprises lithium nickel cobalt manganese oxide;
preferably, the lithium nickel cobalt manganese oxide comprises LiNi0.3Co0.3Mn0.3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2Or LiNi0.8Co0.1Mn0.1O2At least one of (1).
6. A method for preparing a ternary positive electrode material coated with a PTC material according to any one of claims 1 to 5, comprising the steps of:
and uniformly mixing sodium bismuth titanate and the ternary cathode material, and sintering to ensure that the sodium bismuth titanate is uniformly coated on the surface of the ternary cathode material to form the PTC material layer.
7. The method for preparing the ternary cathode material coated with the PTC material according to claim 6, wherein the sintering temperature is 300-700 ℃, and the holding time is 5-7 h;
preferably, the sintering temperature is 400-;
preferably, the rate of temperature increase from room temperature to the sintering temperature is 2.5-3.5 deg.C/min, preferably 3 deg.C/min, prior to sintering.
8. The method for preparing a ternary cathode material coated with a PTC material according to claim 6, wherein the mass ratio of the sodium bismuth titanate to the ternary cathode material is (0.05-0.5): 100, preferably (0.1-0.2): 100.
9. a lithium ion battery positive electrode material, characterized by comprising the PTC material-coated ternary positive electrode material according to any one of claims 1 to 5 or the PTC material-coated ternary positive electrode material prepared by the preparation method according to any one of claims 6 to 8.
10. A lithium ion battery, comprising the ternary cathode material coated with a PTC material according to any one of claims 1 to 5, the ternary cathode material coated with a PTC material prepared by the preparation method according to any one of claims 6 to 8, or the lithium ion battery cathode material provided in claim 9.
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