CN112086618A - High-lithium-ion-conductivity positive plate and preparation method thereof - Google Patents

High-lithium-ion-conductivity positive plate and preparation method thereof Download PDF

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CN112086618A
CN112086618A CN202010917553.9A CN202010917553A CN112086618A CN 112086618 A CN112086618 A CN 112086618A CN 202010917553 A CN202010917553 A CN 202010917553A CN 112086618 A CN112086618 A CN 112086618A
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lithium
positive electrode
lithium manganate
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张秀奎
赵成龙
王正伟
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Xingheng Power Supply Chuzhou Co ltd
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Xingheng Power Supply Chuzhou Co ltd
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Abstract

The invention discloses a high lithium ion conduction positive plate and a preparation method thereof, wherein the positive plate comprises a current collector and a positive electrode layer coated on the current collector, and is characterized in that: the positive electrode layer comprises large-particle lithium manganate, small-particle single crystal positive electrode materials, a fast ion conductor, a conductive agent and a binder, wherein the large-particle lithium manganate is secondary-particle lithium manganate, and D50 is 10-30 mu m; the small-particle single-crystal positive electrode material is single-crystal lithium manganate or single-crystal nickel cobalt lithium manganate, and D50 is 1-5 mu m; the fast ion conductor is one of lithium aluminum titanium phosphate, lithium lanthanum titanate and lithium lanthanum zirconium oxide; the mass ratio of the large-particle lithium manganate to the small-particle single crystal positive electrode material is (2-10) to 1. After the materials are mixed by a dry method, the materials are firstly made into paste, then made into slurry, and finally formed into the anode coating. According to the invention, a lithium ion transmission three-dimensional network of the positive plate is constructed, the polarization and manganese dissolution of lithium manganate are reduced, and the cycle performance is improved.

Description

High-lithium-ion-conductivity positive plate and preparation method thereof
Technical Field
The invention relates to a lithium ion battery, in particular to a positive pole piece for the lithium ion battery and a preparation method of the positive pole piece.
Background
The lithium manganate cathode material has the advantages of rich resources, low cost, high voltage, good rate capability and the like, but generates more Mn in the final stage of discharge3+And the Jahn-Teller effect is easy to occur, and the structure is damaged due to the fact that soluble divalent Mn is generated by disproportionation of trivalent Mn, so that the battery cycle performance is poor when the lithium manganate is used as the lithium ion battery cathode material. Meanwhile, the compaction of the lithium manganate is low, the content of active substances is influenced, the contact between anode materials is reduced, the polarization is increased, the dissolution of manganese ions is further promoted, and the cycle performance is damaged.
The compaction of the lithium manganate can be improved by a method of compounding large and small particles. The Chinese patent publication No. CN103794751A discloses a preparation method of a lithium manganate-based lithium ion battery cathode material, which comprises the steps of mixing modified lithium manganate with different particle sizes, and carrying out surface modification to obtain a lithium manganate finished product. The method improves the volume capacity and the structural stability of the lithium manganate material, improves the cycle performance and the high-temperature performance of the material, but needs multi-step sintering and mixing, has high energy consumption, is difficult to control the product consistency, and is difficult to realize industrial production. The Chinese patent application with publication number CN106532033A discloses a preparation method of a mixed lithium manganate material, which is characterized in that lithium manganate materials with particles of different sizes are respectively prepared and then are mixed to prepare the lithium manganate material with high compaction and high multiplying power. Although the method improves the compaction of the lithium manganate, the improvement effect is limited, the key cycle performance index is not expressed, and the problem of pain points of the lithium manganate is not solved. The Chinese patent application with publication number CN109244450A discloses a preparation method of a high-compaction high-capacity lithium manganate composite positive electrode material for blending ternary materials, which comprises the steps of firstly preparing two lithium manganate positive electrode materials, namely a small-particle lithium manganate material with narrow particle size distribution and a large-particle lithium manganate material with wide particle size distribution, and blending the two lithium manganate positive electrode materials according to a certain proportion, so that the gram volume and the compaction density of the lithium manganate material are improved. However, in the method, more narrow-particle-size small-particle lithium manganate is easy to be overcharged and overcharged, so that the dissolution speed of manganese is increased, and the long-term use of the battery is not facilitated.
In the above technical solution, although the compaction performance of the positive electrode material is improved by compounding the large and small particles, the above technical problems and cost problems exist. Therefore, it is necessary to improve the positive plate made of lithium manganate and provide a new preparation method to obtain the positive plate of lithium ion battery with excellent performance, low cost and easy mass production.
Disclosure of Invention
The invention aims to provide a high-lithium-ion-conductivity positive plate which is convenient for lithium ion transmission and improves the performance of a lithium manganate battery while improving the compaction performance of a positive material. The invention also aims to provide a preparation method of the positive plate.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a high lithium ion conduction positive plate comprises a current collector and a positive electrode layer coated on the current collector, wherein the positive electrode layer comprises large-particle lithium manganate, small-particle single crystal positive electrode materials, a fast ion conductor, a conductive agent and a binder, the large-particle lithium manganate is secondary-particle lithium manganate, and D50 is 10-30 microns; the small-particle single-crystal positive electrode material is single-crystal lithium manganate or single-crystal nickel cobalt lithium manganate, and D50 is 1-5 mu m; the fast ion conductor is one of Lithium Aluminum Titanium Phosphate (LATP), Lithium Lanthanum Titanate (LLTO) and Lithium Lanthanum Zirconium Oxide (LLZO); the mass ratio of the large-particle lithium manganate to the small-particle single crystal positive electrode material is (2-10) to 1.
In the technical scheme, the secondary particle lithium manganate is adopted as a main active substance, is prepared by sintering electrolytic manganese dioxide and lithium carbonate, is low in price, stable in quality and convenient for large-scale production, and has high specific capacity and excellent comprehensive performance; the small-particle single crystal positive electrode material is matched, the lithium ion de-intercalation speed is high, the rate capability can be improved, the energy performance of the large-particle lithium manganate can be complemented, and meanwhile, the single crystallization reduces the specific surface area, so that the structural change caused by the dissolution of transition metals is prevented; by controlling the mass ratio of large particles to small particles, the space utilization rate is improved, and the compaction density is ensured; meanwhile, a fast ion conductor is added to achieve the effect of constructing a lithium ion fast channel.
In a preferred technical scheme, D50 of the small-particle single-crystal cathode material is less than 22% of D50 of the large-particle lithium manganate. To ensure that the small particles enter the interstices of the large particles well.
According to the preferable technical scheme, the mass ratio of the large-particle lithium manganate to the small-particle single crystal positive electrode material is (2-4) to 1.
In the technical scheme, the D50 of the fast ion conductor is 50-500 nm, and the mass of the fast ion conductor is 0.6-3% of the total mass of large-particle lithium manganate and small-particle single crystal positive electrode materials. If the content of the fast ion conductor is low, the effect of constructing a lithium ion fast channel cannot be achieved, the content is unnecessary, the smaller the particle size of the fast ion conductor is, the easier the active material connection is, but the particles are too small to be dispersed, the preparation cost is high, and the size of 50-500 nm can be easily achieved by adopting a mature sand mill.
In the technical scheme, the current collector is an aluminum foil; the conductive agent is one or a mixture of more than two of carbon black conductive agent (sp), graphite conductive agent and Carbon Nano Tubes (CNTs), and the binder is one or a mixture of polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE).
In order to realize another purpose of the invention, the invention discloses a preparation method of a high lithium ion conduction positive plate, which comprises the steps of adding large-particle lithium manganate, small-particle single crystal positive electrode materials, a fast ion conductor, a conductive agent and a binder into a stirrer, stirring at a low speed and mixing in a dry method, then adding N-methyl pyrrolidone to mix the materials into a viscous paste, continuously adding N-methyl pyrrolidone and stirring at a high speed to mix the materials into slurry, coating the slurry on a current collector and drying, and rolling to obtain the high lithium ion conduction positive plate.
In the technical scheme, the solid content of the slurry is 45-75% by controlling the addition of the N-methyl pyrrolidone. The solid substances are mixed by a dry method, when the N-methyl pyrrolidone is added, a two-step adding method is adopted, a paste mixture is prepared firstly, and then the paste is prepared, so that the fast nano ion conductor can be fully dispersed among the active substances, and the agglomeration is avoided.
In the technical scheme, the density of the coating surface on the current collector is 120-300 g/m2The compaction density is 3.1-3.4 g/cm3. The mixing of the size particles allows the same volume to hold more active material, increasing the compaction density, while the higher compaction density increases the contact of the fast ion conductor with the active material, further increasing the transport of lithium ions.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. according to the invention, large-particle lithium manganate, small-particle single crystal positive electrode materials and nano fast ion conductors are creatively mixed for use and are in close contact under the high-pressure effect, so that a lithium ion transmission three-dimensional network of a positive plate is constructed, the polarization and manganese dissolution of lithium manganate are reduced, and the cycle performance is improved;
2. according to the invention, the proportion and the particle diameter ratio of the doped large-particle lithium manganate and small-particle single crystal positive electrode material are controlled, gaps among large particles are fully utilized, the compaction density is improved, and the contact between a fast ion conductor and an active substance is further improved by high compaction;
3. according to the invention, the lithium manganate with secondary particles is adopted to provide energy, the lithium manganate is cheap and easy to obtain, the small-particle material is adopted to increase the lithium ion de-intercalation speed, improve the rate capability, reduce the specific surface area by single crystallization, enhance the structural stability and improve the cycle performance;
4. in the preparation process, a dry mixing method of solid substances is adopted, and a paste mixture is prepared firstly, so that the full dispersion of the fast nano-ion conductor can be ensured.
Drawings
Fig. 1 is a cycle life diagram of a square aluminum cell prepared in example 1;
fig. 2 is a cycle life diagram of a square aluminum can cell prepared in comparative example 1;
fig. 3 is a cycle life diagram of a square aluminum can cell prepared in comparative example 2.
Detailed Description
The invention is further described with reference to the following figures and examples:
example 1:
4 kg of lithium manganate, 1 kg of single crystal lithium nickel cobalt manganese, 0.06 kg of LATP, 0.053 kg of sp, 0.105 kg of CNTs and 0.105 kg of PVDF were added to a 10L planetary mixer, and the particle size of lithium manganate was 16 μm, and the particle size of single crystal lithium nickel cobalt manganese was 523 type, 3 μm. And (3) revolving the stirrer for 15r/min, stirring for 1 hour, adding 1 kg of NMP, stirring for 1 hour again, mixing the materials into a viscous paste, adding 2.3 kg of NMP, increasing the revolution to 35r/min, starting a dispersion disc, gradually increasing the revolution speed to 1000r/min at 300r/min, and stirring for 2 hours at a high speed to obtain uniform anode slurry. Coating the slurry on an aluminum foil with the thickness of 15 mu m and drying the aluminum foil, wherein the coating surface density is 250g/m2And tabletting by a roller press to ensure that the compacted density of the pole piece is 3.4g/cm3And obtaining the positive plate with high lithium ion conduction.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 22.3Ah, and 86.4 percent of capacity is remained after the battery is cycled for 800 times at normal temperature. The cycle life test curve is shown in figure 1.
Example 2:
4 kg of lithium manganate, 1 kg of single-crystal lithium nickel cobalt manganese, 0.15 kg of LLTO, 0.053 kg of sp, 0.105 kg of CNTs and 0.105 kg of PVDF were added to a 10L planetary mixer, and the particle size of lithium manganate was 10 μm, and the particle size of single-crystal lithium nickel cobalt manganese was 523 type, 1 μm. And (3) revolving the stirrer for 15r/min, stirring for 1 hour, adding 1 kg of NMP, stirring for 1 hour again, mixing the materials into a viscous paste, adding 2.3 kg of NMP, increasing the revolution to 35r/min, starting a dispersion disc, gradually increasing the revolution speed to 1000r/min at 300r/min, and stirring for 2 hours at a high speed to obtain uniform anode slurry. Coating the slurry on an aluminum foil with the thickness of 15 mu m and drying the aluminum foil, wherein the coating surface density is 250g/m2Roller pressThe pole piece is pressed into pieces to ensure that the compaction density of the pole piece is 3.15g/cm3And obtaining the positive plate with high lithium ion conduction.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 22.0Ah, and 85.5 percent of capacity is remained after the battery is cycled for 800 times at normal temperature.
Example 3:
3.33 kg of lithium manganate, 1.67 kg of single crystal lithium nickel cobalt manganese oxide, 0.03 kg of LLZO, 0.053 kg of sp, 0.105 kg of conductive graphite ks-6 and 0.105 kg of PTFE were put into a 10L planetary mixer, and the particle size of lithium manganate was 16 μm, and the particle size of single crystal lithium nickel cobalt manganese oxide was 523 type, 3 μm. And (3) revolving the stirrer for 15r/min, stirring for 1 hour, adding 1 kg of NMP, stirring for 1 hour again, mixing the materials into a viscous paste, adding 2.3 kg of NMP, increasing the revolution to 35r/min, starting a dispersion disc, gradually increasing the revolution speed to 1000r/min at 300r/min, and stirring for 2 hours at a high speed to obtain uniform anode slurry. Coating the slurry on a 15 mu m aluminum foil and drying the aluminum foil, wherein the coating surface density is 120g/m2And tabletting by a roller press to ensure that the compacted density of the pole piece is 3.4g/cm3And obtaining the positive plate with high lithium ion conduction.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 22.6Ah, and 92.0 percent of capacity is remained after the battery is cycled for 800 times at normal temperature.
Example 4:
4.5 kg of lithium manganate, 0.5 kg of single-crystal lithium manganate, 0.06 kg of LATP, 0.053 kg of sp, 0.105 kg of CNTs and 0.105 kg of PVDF were put into a 10-liter planetary mixer, and the particle diameter of lithium manganate was 30 μm and that of single-crystal lithium manganate was 5 μm. And (3) revolving the stirrer for 15r/min, stirring for 1 hour, adding 1 kg of NMP, stirring for 1 hour again, mixing the materials into a viscous paste, adding 2.3 kg of NMP, increasing the revolution to 35r/min, starting a dispersion disc, gradually increasing the revolution speed to 1000r/min at 300r/min, and stirring for 2 hours at a high speed to obtain uniform anode slurry. Coating the slurry on a 15 mu m aluminum foil and drying the aluminum foil, wherein the coating surface density is 300g/m2And tabletting by a roller press to ensure that the compacted density of the pole piece is 3.1g/cm3And obtaining the positive plate with high lithium ion conduction.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 21.5Ah, and 76.3 percent of capacity is remained after the battery is cycled for 800 times at normal temperature.
Comparative example 1:
4 kg of lithium manganate, 1 kg of lithium nickel cobalt manganate, 0.053 kg of sp, 0.105 kg of CNTs and 0.105 kg of PVDF were added into a 10L planetary mixer, wherein the particle size of lithium manganate is 16 μm, and the particle size of lithium nickel cobalt manganate is 523 type and is 15 μm. And (3) revolving the stirrer for 15r/min, stirring for 1 hour, adding 1 kg of NMP, stirring for 1 hour again, mixing the materials into a viscous paste, adding 2.3 kg of NMP, increasing the revolution to 35r/min, starting a dispersion disc, gradually increasing the revolution speed to 1000r/min at 300r/min, and stirring for 2 hours at a high speed to obtain uniform anode slurry. Coating the slurry on an aluminum foil with the thickness of 15 mu m and drying the aluminum foil, wherein the coating surface density is 250g/m2And tabletting by a roller press to ensure that the compacted density of the pole piece is 3.0g/cm3And obtaining the positive plate for comparison.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery, the thickness is 21mm, the width is 115mm, the height is 108mm, the designed capacity is 21.6Ah, and 82.4 percent of capacity is remained after the battery is cycled for 800 times at normal temperature. The cycle life test curve is shown in figure 2.
Comparative example 2:
5.0 kg of lithium manganate having a particle size of 30 μm, 0.053 kg of sp, 0.105 kg of CNTs and 0.105 kg of PVDF were put into a 10L planetary mixer. And (3) revolving the stirrer for 15r/min, stirring for 1 hour, adding 1 kg of NMP, stirring for 1 hour again, mixing the materials into a viscous paste, adding 2.3 kg of NMP, increasing the revolution to 35r/min, starting a dispersion disc, gradually increasing the revolution speed to 1000r/min at 300r/min, and stirring for 2 hours at a high speed to obtain uniform anode slurry. The slurry was coated on a 15 μm aluminum foil and dried, the coated surface density was 230g/m2, and the sheet was pressed by a roll press so that the sheet had a compacted density of 2.95g/cm3, giving a comparative positive sheet.
The prepared pole piece is assembled into a square aluminum shell lithium ion battery with the thickness of 21mm, the width of 115mm, the height of 108mm, the designed capacity of 21.6Ah, and 71.2 percent of capacity remained after the battery is cycled for 600 times at normal temperature. The cycle life test curve is shown in figure 3.

Claims (8)

1. The utility model provides a high lithium ion switches on positive plate, includes the mass flow body and coats the positive plate on the mass flow body, its characterized in that: the positive electrode layer comprises large-particle lithium manganate, small-particle single crystal positive electrode materials, a fast ion conductor, a conductive agent and a binder, wherein the large-particle lithium manganate is secondary-particle lithium manganate, and D50 is 10-30 mu m; the small-particle single-crystal positive electrode material is single-crystal lithium manganate or single-crystal nickel cobalt lithium manganate, and D50 is 1-5 mu m; the fast ion conductor is one of lithium aluminum titanium phosphate, lithium lanthanum titanate and lithium lanthanum zirconium oxide; the mass ratio of the large-particle lithium manganate to the small-particle single crystal positive electrode material is (2-10) to 1.
2. The high lithium ion conducting positive electrode sheet according to claim 1, characterized in that: the D50 of the small-particle single-crystal positive electrode material is less than 22% of the D50 of the large-particle lithium manganate.
3. The high lithium ion conducting positive electrode sheet according to claim 1, characterized in that: the mass ratio of the large-particle lithium manganate to the small-particle single crystal positive electrode material is (2-4) to 1.
4. The high lithium ion conducting positive electrode sheet according to claim 1, characterized in that: the D50 of the fast ion conductor is 50-500 nm, and the mass of the fast ion conductor is 0.6-3% of the total mass of the large-particle lithium manganate and the small-particle single crystal positive electrode material.
5. The high lithium ion conducting positive electrode sheet according to claim 1, characterized in that: the current collector is an aluminum foil; the conductive agent is one or a mixture of more than two of carbon black conductive agent, graphite conductive agent and carbon nano tubes, and the binder is one or a mixture of polyvinylidene fluoride and polytetrafluoroethylene.
6. The method for preparing the high lithium ion conduction positive plate according to any one of claims 1 to 5, characterized in that: adding large-particle lithium manganate, small-particle single crystal positive electrode materials, a fast ion conductor, a conductive agent and a binder into a stirrer, stirring at a low speed and mixing in a dry method, then adding N-methyl pyrrolidone to enable the materials to be mixed into a viscous paste, continuously adding N-methyl pyrrolidone and stirring at a high speed to enable the materials to be mixed into slurry, coating the slurry on a current collector and drying, and rolling to obtain the high-lithium-ion-conduction positive electrode plate.
7. The method for preparing the high lithium ion conducting positive plate according to claim 6, wherein the method comprises the following steps: the solid content of the slurry is 45-75%.
8. The method for preparing the high lithium ion conducting positive plate according to claim 6, wherein the method comprises the following steps: the density of the coating surface on the current collector is 120-300 g/m2The compaction density is 3.1-3.4 g/cm3。
CN202010917553.9A 2020-09-03 2020-09-03 High-lithium-ion-conductivity positive plate and preparation method thereof Pending CN112086618A (en)

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