CN121583916B - Multicomponent positive electrode active material, lithium ion battery positive electrode, preparation method of multicomponent positive electrode active material and high-rate lithium ion battery - Google Patents
Multicomponent positive electrode active material, lithium ion battery positive electrode, preparation method of multicomponent positive electrode active material and high-rate lithium ion batteryInfo
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Abstract
The invention discloses a multi-component positive electrode active material, a lithium ion battery positive electrode, a preparation method of the multi-component positive electrode active material and a high-rate lithium ion battery, and belongs to the technical field of lithium ion batteries. The multi-component positive electrode active material comprises lithium iron manganese phosphate, spinel type oxide, superconductive carbon black, nano carbon fiber and nano Li 2Al2B2O7 powder. According to the invention, the particle size proportion and the mass ratio of different materials are controlled, the electronic conductivity in the anode material is improved in a particle gap filling mode, and a continuous three-dimensional conductive network is constructed, so that the problem of weak rate performance caused by low electronic conductivity and ion conductivity is solved, the conductivity of the three-dimensional conductive network is enhanced, the electrode polarization is reduced, and the high rate discharge performance is finally realized.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a multi-component positive electrode active material, a lithium ion battery positive electrode, a preparation method of the multi-component positive electrode active material and a high-rate lithium ion battery.
Background
Lithium iron manganese phosphate (LMFP) has the advantages of high safety of lithium iron phosphate and high voltage of lithium manganese phosphate, and becomes a preferable positive electrode material of a high-rate battery, but two key bottlenecks exist, namely, the conduction performance of electrons and ions is insufficient, the reason is that the LMFP is low in electron conductivity and small in lithium ion diffusion coefficient, a single material is difficult to meet the charge transmission requirement under high rate, the existing conductive agent (such as SP) is mostly added randomly, a continuous conduction network cannot be formed, and the electron transmission resistance is large. Secondly, the compaction density and the porosity of the LMFP have process design contradiction, the compaction density of the traditional LMFP positive electrode is only 2.4g/cm < 3 > because particles are loosely piled (mostly single particle diameter or disordered mixture), if the compaction density is forcedly increased, too low porosity is easily caused, electrolyte cannot be fully infiltrated and aggravate ion transmission resistance, finally the situation of 'diving' when the battery is used due to overlarge internal resistance is caused, if the high porosity is reserved, the energy density is sacrificed, the internal resistance of contact between particles is also increased, and the two situations form the situation of 'multiplying power-energy'.
In the prior art, although there is an attempt to improve the performance by spinel oxide or adding metal powder, there are obvious defects that, firstly, no pole matching design is performed for the particle size, spinel particles and LMFP particles are not matched in size and cannot effectively fill gaps, secondly, a cooperative design of gap filling-high compaction-conductive network is lacked, the traditional design focuses on material components only, the influence of the structure on the performance is ignored, the electronic conductivity after compaction is improved, the internal resistance of a battery is not remarkably improved, and the conductivity and the cycle performance are reduced even because particles are crushed.
Disclosure of Invention
The invention aims to solve the technical problems of providing a multi-component positive electrode active material, a lithium ion battery positive electrode, a preparation method thereof and a high-rate lithium ion battery, wherein a continuous electron-ion conduction network is constructed through a technical route of multi-component positive electrode grading design and accurate filling of particle gaps, the electron conductivity and the ion conductivity are improved, and finally, the high-rate discharge performance is realized.
To solve the above technical problems, according to one aspect of the present invention, there is provided a multi-component positive electrode active material including lithium iron manganese phosphate, spinel-type oxide, superconductive carbon black, nano carbon fiber, and nano Li 2Al2B2O7 powder, wherein the spinel-type oxide is at least one of LiMn 2O4 or LiNi 0.5Mn1.5O4;
The particle size ratio of the lithium iron manganese phosphate to the spinel-type oxide to the superconductive carbon black is 1:0.4-0.5:0.15-0.16, and the mass ratio is 60.0-60.5:4.5-5.0:0.23-0.24.
In a preferred embodiment, the particle size of the lithium manganese iron phosphate is 4-20 μm.
In a preferred embodiment, the particle size of the superconducting carbon black is 0.15 to 0.8 μm.
As a preferable embodiment, the fiber diameter of the nano carbon fiber is 20-100nm, and the particle size of nano Li 2Al2B2O7 powder is 0.01-0.2 μm.
As a preferred embodiment, the mass ratio of the nano carbon fiber to nano Li 2Al2B2O7 powder is 1:3.
According to another aspect of the present invention, there is provided a lithium ion battery positive electrode comprising the above-described multi-component positive electrode active material and a binder.
According to another aspect of the present invention, there is provided a method for preparing the positive electrode of a lithium ion battery described above, comprising:
step one, dispersing components of a multi-component positive electrode active material to form a positive electrode material mixture;
Step two, mixing and dispersing the anode material mixture and PVDF glue solution to form slurry;
and thirdly, coating the slurry on an aluminum foil, and drying and slicing to prepare the anode of the lithium ion battery.
In a preferred embodiment, the PVDF adhesive is mixed with N-methylpyrrolidone, and stirred to form the PVDF glue solution described in the second step.
According to another aspect of the present invention, there is provided the use of the positive electrode of a lithium ion battery described above in the preparation of a lithium ion battery.
According to another aspect of the invention, there is provided a high rate lithium ion battery comprising a positive electrode, a separator, a liquid electrolyte and a negative electrode, the positive electrode being the positive electrode of the lithium ion battery described above.
The positive electrode active material provided by the invention has the advantages that the particle size proportion and the mass ratio of different materials are controlled, the electronic conductivity in the positive electrode material is improved in a particle gap filling mode, and meanwhile, a continuous three-dimensional conductive network is constructed, so that the problem of weak rate performance caused by low electronic conductivity and ionic conductivity is solved, the conductivity of the three-dimensional conductive network is enhanced, and the polarization of an electrode is reduced. The spinel type composite oxide can inhibit LMFP lattice distortion and optimize cycle performance.
The lithium ion battery prepared by the method disclosed by the invention has the advantages that the high-rate performance is improved, the cycle performance is not reduced, the 10C discharge capacity retention rate is more than or equal to 90%, and the lithium ion battery is superior to the traditional LMFP battery (the 10C discharge capacity retention rate is less than or equal to 60%).
The lithium ion battery provided by the invention is suitable for the fields of fast-charging new energy automobiles, unmanned aerial vehicles, emergency power supplies and the like.
Drawings
FIG. 1 is a schematic view of the particle distribution inside a positive electrode active material of the present invention;
fig. 2 is a ratio performance comparison of lithium ion batteries prepared in example 1 and comparative examples 1 and 2;
fig. 3 is a comparison of cycle performance of lithium ion batteries prepared in example 2 and comparative examples 3 and 4;
Fig. 4 is a comparison of the dc internal resistance performance of the lithium ion batteries prepared in example 3 and comparative examples 5 and 6.
Detailed Description
The basic concept of the invention is to adopt a multi-component positive electrode grading design and a technical idea of precisely filling particle gaps, to fill the gaps between large particles by utilizing small particles to improve compaction and shorten the contact distance between the particles and to improve electronic conductivity and ionic conductivity by controlling the particle size proportion, the volume ratio and the mass ratio of different materials, to further construct a high-efficiency three-dimensional conductive network, and to optimize a negative electrode SEI film by matching with an improved battery pre-formation process, so as to solve the high-rate bottleneck of the LMFP-based battery from the structural aspect.
Based on the above conception, the multi-component positive electrode active material provided by the typical embodiment of the invention adopts a multi-component pole distribution design mode, and comprises lithium manganese iron phosphate (LiMn xFe1-xPO4, X is more than or equal to 0.4 and less than or equal to 0.6, and is abbreviated as LMFP), spinel type oxide, superconducting carbon black (SP), nano carbon fiber and nano Li 2Al2B2O7 powder, wherein the spinel type oxide is at least one of LiMn 2O4 or LiNi 0.5Mn1.5O4.
As shown in fig. 1, in the present embodiment, lithium iron manganese phosphate and spinel-type oxide (LiMn 2O4/LiNi0.5Mn1.5O4) with spherical particle morphology and uniform particle size are used as main bodies, superconducting carbon black, carbon nanofibers and Li 2Al2B2O7 powder with specific particle size are compounded, and the particle size ratio, mass ratio and volume ratio of the above materials are controlled to realize close packing among the particles of the positive electrode powder.
In the embodiment, the particle size ratio of the lithium iron manganese phosphate, the spinel-type oxide and the superconducting carbon black is 1:0.4-0.5:0.15-0.16, and the mass ratio is 60.0-60.5:4.5-5.0:0.23-0.24.
The lithium iron manganese phosphate is a large particle main body, the spinel type oxide material fills primary gaps among LMFP particles in a particle gap filling mode, and the superconductive carbon black fills secondary gaps formed by the lithium iron manganese phosphate and the spinel type oxide material, so that close packing among anode powder particles is realized. The spinel type composite oxide inhibits LMFP lattice distortion, optimizes cycle performance, fills the residual tiny gaps with nano carbon fiber and nano Li 2Al2B2O7 powder, remarkably improves electron conductivity and ion conductivity of the electrode in a mode of constructing an electron and ion three-dimensional conductive network, and further remarkably improves the rate performance of the battery.
Illustratively, the particle size ratio of lithium manganese phosphate, spinel oxide, superconductive carbon black may be 1:0.4:0.15, 1:0.5:0.16, 1:0.45:0.156, and the mass ratio may be 60.0:4.5:0.23, 60.5:5.0:0.24, 60.25:4.85:0.235.
Illustratively, in a preferred embodiment, the particle size ratio of lithium manganese iron phosphate, spinel-type oxide and superconducting carbon black is strictly controlled to be 1:0.414:0.154, and the mass ratio is 60.318: 4.871:0.235, so that the three materials are ensured to realize close packing, and the volume ratio of the space occupied by the three materials is 16.755:1.188:0.124. The particle size of the lithium iron manganese phosphate is 4-20 mu m, and the lithium iron manganese phosphate is ensured to serve as a stacking basis of main particles. The particle size of the lithium iron manganese phosphate may be, for example, 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, 15 μm, 18 μm, 20 μm.
The particle size of the spinel oxide material (LiMn 2O4/LiNi0.5Mn1.5O4) is 0.8-10 mu m, and the requirement of primary gap filling is met. Illustratively, the particle size of the spinel oxide material may be 0.8 μm, 1.0 μm, 1.2 μm, 1.6 μm, 2 μm, 5 μm, 8 μm,10 μm.
In the spinel oxide material, the mass ratio of LiMn 2O4、LiNi0.5Mn1.5O4 to LiMn is preferably 1:1.
The particle size of the superconducting carbon black is 0.15-0.8 mu m, the conductivity is more than or equal to 100S/m, the secondary gap filling is realized, and a continuous electron conduction path is constructed. Illustratively, the particle size of the superconductive carbon black is 0.15 μm, 0.2 μm, 0.3 μm, 0.5 μm, 0.8 μm.
The carbon nanofibers have a fiber diameter of 20-100nm, and illustratively, the carbon nanofibers may have a fiber diameter of 20nm, 30nm, 50nm, 80nm, 100nm.
The particle size of the nano Li 2Al2B2O7 powder is 0.01-0.2 μm, and the particle size of the nano Li 2Al2B2O7 powder may be 0.01 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.15 μm, 0.2 μm, for example.
The mass ratio of the nano carbon fiber to the nano Li 2Al2B2O7 powder is preferably 1:3, so as to improve the electronic conductivity and the ionic conductivity.
Another exemplary embodiment of the present invention provides a lithium ion battery positive electrode prepared based on the above multi-component active material, and the preparation method thereof includes the steps of:
step one, preparing a positive electrode material mixture
The components of the multi-component positive electrode active material described in the above embodiments are mixed and dispersed to form a positive electrode material mixture.
In the step, firstly, lithium iron manganese phosphate and spinel type oxide are stirred and dispersed uniformly to form an anode active material, and then superconducting carbon black, nano carbon fiber and nano Li 2Al2B2O7 powder are compounded and added into the uniformly mixed anode active material to form an anode material mixture, and the anode material mixture is stirred and dispersed uniformly.
Step two, preparing positive electrode slurry
And mixing and dispersing the positive electrode material mixture and the PVDF glue solution to form slurry with the solid content of 50% -65%.
The glue solution is formed by mixing and stirring a PVDF binder and N-methyl pyrrolidone, and the mixing ratio of the PVDF binder to the N-methyl pyrrolidone is preferably 6:94. The mass ratio of the positive electrode material mixture to the PVDF glue solution is preferably 96-99:1-4.
Step three, preparing the anode of the lithium ion battery
And (3) drying and slicing the anode slurry on aluminum foil with the thickness of 10-12 mu m to prepare the anode of the lithium ion battery.
In another exemplary embodiment of the present invention, a lithium ion battery is provided that includes a positive electrode, a separator, a liquid electrolyte, and a negative electrode.
The positive electrode is a lithium ion positive electrode prepared based on the multi-component positive electrode active material.
Mixing graphite, a conductive agent, sodium carboxymethyl cellulose and styrene-butadiene rubber according to a proportion to prepare uniformly mixed slurry, and then coating, rolling, drying and slicing the slurry on copper foil with the thickness of 6-12 mu m to prepare the negative electrode.
And laminating the positive electrode, the diaphragm and the negative electrode in an alternating sequence of the positive electrode, the diaphragm, the negative electrode and the positive electrode, or winding the laminated diaphragm, the positive electrode, the diaphragm and the negative electrode to manufacture a battery core, and then carrying out tab welding and aluminum plastic film packaging on the battery core.
The battery cell is baked, and the purpose is to remove the redundant water in the battery cell, electrolyte is injected after baking, and then the battery cell is placed still after the electrolyte is injected.
Finally, performing operations such as preforming, high-temperature aging, OCV testing, normal-temperature aging and the like on the battery cell, and obtaining an improved battery sample.
The pre-formation is to use a small current system of 0.01C, 0.02C, 0.05C and 0.1C for battery activation and charging, and aims to form a compact SEI film at the initial stage, thereby being beneficial to the optimization of multiplying power and cycle performance.
The following examples are provided to further illustrate the claimed invention. However, examples and comparative examples are provided for the purpose of illustrating embodiments of the present invention and do not exceed the scope of the inventive subject matter, which is not limited by the examples. Unless specifically indicated otherwise, materials and reagents used in the present invention are available from commercial products in the art.
Example 1
And (1) stirring and dispersing the LMFP and the LiMn 2O4 uniformly to form an anode active material, and then adding the SP, the nano carbon fiber and the nano Li 2Al2B2O7 powder into the uniformly mixed anode active material, and stirring and dispersing uniformly to obtain an anode material mixture.
And (2) mixing and stirring the PVDF adhesive and N-methylpyrrolidone to obtain PVDF glue solution. And adding the positive electrode material mixture into PVDF glue solution, and uniformly dispersing for 5 hours to form positive electrode slurry with the solid content of 55%.
The mass ratio of the LMFP, the LiMn 2O4, the SP, the nano carbon fiber, the nano Li 2Al2B2O7 powder and the PVDF glue solution is 60.25:4.85:0.235:8.0:24:2.665.
The particle size of LMFP is 4 μm, liMn 2O4 is 1.6 μm, SP is 0.6 μm, the fiber diameter of nano carbon fiber is50 nm, and the particle size of nano Li 2Al2B2O7 powder is 0.1 μm.
And (3) coating the positive electrode slurry on an aluminum foil with the thickness of 10 mu m to form a positive electrode plate with the double-sided density of 35.2+/-0.6 mg/cm 2, rolling the dried positive electrode plate with 2.4g/cm 3, and sequentially carrying out the working procedures of slitting, punching, baking and the like on the electrode plate after rolling.
And (4) mixing graphite, SP, sodium carboxymethylcellulose and styrene-butadiene rubber according to a proportion to prepare uniformly mixed slurry, then coating the slurry on copper foil with the thickness of 6 mu m, and rolling, drying and slicing the coated slurry to prepare the negative electrode plate.
And (5) manufacturing a secondary lithium ion battery core pack by adopting a winding method, welding and packaging the electrode lugs, wherein the packaging shell can be an aluminum plastic film shell. Baking the battery cell, removing excessive water in the battery cell, injecting electrolyte after baking, and then standing after injecting the electrolyte.
And (6) finally, performing operations such as preforming, high-temperature aging, OCV testing, normal-temperature aging and the like on the battery cell to obtain a lithium ion battery sample, wherein the lithium ion battery sample is marked as 1-a.
The pre-formation system comprises (1) standing for 5min, (2) sequentially executing 0.01C constant current charging for 2h, 0.02C constant current charging for 2h and 0.05C constant current charging for 2h, (3) 0.1C constant current constant voltage charging to 4.2V and cut-off current of 0.05C, (4) standing for 5min and 0.1C constant current discharging to 3.0V, (5) 0.2C constant current constant voltage charging to 3.6V and cut-off current of 0.05C, and (6) battery offline.
Comparative example 1
The difference from example 1 is that LiMn 2O4 was not added to the positive electrode material mixture provided in step (1). The remaining steps were the same, and the obtained lithium ion battery samples were designated 1-b.
Comparative example 2
The difference from example 1 is that no carbon nanofibers and no Li 2Al2B2O7 powder were added to the positive electrode material mixture provided in step (1). The remaining steps were the same, and the obtained lithium ion battery samples were designated 1-c.
The liquid lithium ion battery samples prepared in the embodiment 1 and the comparative examples 1 and 2 are fully charged by charging and discharging current of 1C in a 3.0-4.2V interval, and then are subjected to multiplying power test by discharging current of 0.1C, 0.5C, 1C, 2C, 3C and 10C, and compared data are shown in figure 2, so that the liquid lithium ion battery has better multiplying power discharging performance, and the multiplying power discharging performance of 10C is more than or equal to 90%.
Example 2
And (1) stirring and dispersing the LMFP and the LiNi 0.5Mn1.5O4 uniformly to form an anode active material, and then adding the SP, the nano carbon fiber and the nano Li 2Al2B2O7 powder into the uniformly mixed anode active material, and stirring and dispersing uniformly to obtain an anode material mixture.
And (2) mixing and stirring the PVDF adhesive and N-methylpyrrolidone to obtain PVDF glue solution. And adding the positive electrode material mixture into PVDF glue solution, and uniformly dispersing for 5 hours to form positive electrode slurry with the solid content of 50%.
The mass ratio of the LMFP, the LiNi 0.5Mn1.5O4, the SP, the nano carbon fiber, the nano Li 2Al2B2O7 powder and the PVDF glue solution is 60.25:4.85:0.235:8.0:24:2.665.
The particle size of LMFP is 4 μm, liMn 2O4 is 1.6 μm, SP is 0.6 μm, the fiber diameter of nano carbon fiber is 50nm, and the particle size of nano Li 2Al2B2O7 powder is 0.1 μm.
And (3) coating the positive electrode slurry on an aluminum foil with the thickness of 12 mu m to form a positive electrode plate with the double-sided density of 35.2+/-0.6 mg/cm 2, rolling the dried positive electrode plate with 2.4g/cm 3, and sequentially carrying out the working procedures of slitting, punching, baking and the like on the electrode plate after rolling.
And (4) mixing graphite, SP, sodium carboxymethylcellulose and styrene-butadiene rubber according to a proportion to prepare uniformly mixed slurry, then coating the slurry on copper foil with the thickness of 12 mu m, and rolling, drying and slicing the coated slurry to prepare the negative electrode plate.
And (5) manufacturing a secondary lithium ion battery core pack by adopting a winding method, welding and packaging the electrode lugs, wherein the packaging shell can be an aluminum plastic film shell. Baking the battery cell, removing excessive water in the battery cell, injecting electrolyte after baking, and then standing after injecting the electrolyte.
And (6) finally, performing operations such as preforming, high-temperature aging, OCV testing, normal-temperature aging and the like on the battery cell to obtain a lithium ion battery sample, which is marked as 2-a.
The pre-formation system comprises (1) standing for 5min, (2) sequentially executing 0.01C constant current charging for 2h, 0.02C constant current charging for 2h and 0.05C constant current charging for 2h, (3) 0.1C constant current constant voltage charging to 4.2V and cut-off current of 0.05C, (4) standing for 5min and 0.1C constant current discharging to 3.0V, (5) 0.2C constant current constant voltage charging to 3.6V and cut-off current of 0.05C, and (6) battery offline.
Comparative example 3
The difference from example 2 is that LiNi 0.5Mn1.5O4 was not added to the positive electrode material mixture provided in step (1). The remaining steps were the same, and the obtained lithium ion battery sample was designated as 2-b.
Comparative example 4
The difference from example 2 is that no carbon nanofibers and no Li 2Al2B2O7 powder were added to the positive electrode material mixture provided in step (1). The remaining steps were the same, and the obtained lithium ion battery sample was designated as 2-c.
The liquid lithium ion battery samples prepared in the embodiment 2 and the comparative examples 3 and 4 are fully charged with 1C charge and discharge current in the interval of 3.0-4.2V and then are subjected to cycle test with 1C discharge current, and the comparison data are shown in figure 3, so that the liquid lithium ion battery has better normal-temperature cycle performance.
Example 3
And (1) uniformly stirring and dispersing the mixture of the LMFP and the LiMn 2O4/LiNi0.5Mn1.5O4 (the mass ratio of the mixture to the LiMn 2O4/LiNi0.5Mn1.5O4 is 1:1) to form an anode active material, and then adding the SP, the nano carbon fiber and the nano Li 2Al2B2O7 powder into the uniformly mixed anode active material, and uniformly stirring and dispersing to obtain an anode material mixture.
And (2) mixing and stirring the PVDF adhesive and N-methylpyrrolidone to obtain PVDF glue solution. And adding the positive electrode material mixture into PVDF glue solution, and uniformly dispersing for 5 hours to form positive electrode slurry with the solid content of 50%.
The mass ratio of the LMFP, the LiMn 2O4/LiNi0.5Mn1.5O4 mixture, the SP, the nano carbon fiber, the nano Li 2Al2B2O7 powder and the PVDF glue solution is 60.25:4.85:0.235:8.0:24:2.665.
The particle size of LMFP is 4 μm, liMn 2O4 is 1.6 μm, SP is 0.6 μm, the fiber diameter of nano carbon fiber is 50nm, and the particle size of nano Li 2Al2B2O7 powder is 0.1 μm.
And (3) coating the positive electrode slurry on an aluminum foil with the thickness of 12 mu m to form a positive electrode plate with the double-sided density of 35.2+/-0.6 mg/cm 2, rolling the dried positive electrode plate with 2.4g/cm 3, and sequentially carrying out the working procedures of slitting, punching, baking and the like on the electrode plate after rolling.
And (4) mixing graphite, SP, sodium carboxymethylcellulose and styrene-butadiene rubber according to a proportion to prepare uniformly mixed slurry, then coating the slurry on a copper foil with the thickness of 10 mu m, and rolling, drying and slicing the coated slurry to prepare the negative electrode plate.
And (5) manufacturing a secondary lithium ion battery core pack by adopting a lamination method, welding and packaging the electrode lugs, wherein the packaging shell can be an aluminum plastic film shell. Baking the battery cell, removing excessive water in the battery cell, injecting electrolyte after baking, and then standing after injecting the electrolyte.
And (6) finally, performing operations such as preforming, high-temperature aging, OCV testing, normal-temperature aging and the like on the battery cell to obtain a lithium ion battery sample, which is marked as 3-a.
The pre-formation system comprises (1) standing for 5min, (2) sequentially executing 0.01C constant current charging for 2h, 0.02C constant current charging for 2h and 0.05C constant current charging for 2h, (3) 0.1C constant current constant voltage charging to 4.2V and cut-off current of 0.05C, (4) standing for 5min and 0.1C constant current discharging to 3.0V, (5) 0.2C constant current constant voltage charging to 3.6V and cut-off current of 0.05C, and (6) battery offline.
Comparative example 5
The difference from example 3 is that LiMn 2O4/LiNi0.5Mn1.5O4 was not added to the positive electrode material mixture provided in step (1). The remaining steps were the same, and the obtained lithium ion battery sample was designated 3-b.
Comparative example 6
The difference from example 3 is that no carbon nanofibers and no Li 2Al2B2O7 powder were added to the positive electrode material mixture provided in step (1). The remaining steps were the same, and the obtained lithium ion battery sample was designated 3-c.
The liquid lithium ion battery samples prepared in example 3 and comparative examples 5 and 6 were subjected to 15S charge and discharge tests with a charge and discharge current of 2C in the interval of 3.0-4.2V, and the comparative data are shown in fig. 4, which shows that the liquid lithium ion battery of the present invention has lower dc internal resistance.
The scope of the present invention is not limited to the above embodiments, but various modifications and alterations of the present invention will become apparent to those skilled in the art, and any modifications, improvements and equivalents within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
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