CN112786891A - Electrode material, electrode plate, preparation method of electrode plate and lithium ion battery - Google Patents

Electrode material, electrode plate, preparation method of electrode plate and lithium ion battery Download PDF

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CN112786891A
CN112786891A CN202110126075.4A CN202110126075A CN112786891A CN 112786891 A CN112786891 A CN 112786891A CN 202110126075 A CN202110126075 A CN 202110126075A CN 112786891 A CN112786891 A CN 112786891A
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electrode
ion conductor
fast ion
lithium
additive
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占克军
王恒
李晓玲
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Dongguan Weike Battery Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides an electrode material, an electrode plate, a preparation method of the electrode plate and a lithium ion battery, and the electrode material, the electrode plate and the preparation method of the electrode plate comprise an active material and a fast ion conductor additive (FIC), wherein the fast ion conductor additive is Li2O‑Al2O3‑MaOb‑SiO2‑P2O5Wherein M is Ti and/or Ge, 0<a≤2，0<b is less than or equal to 3. Compared with the prior art, the electrode material provided by the invention adopts the novel compound obtained by various oxides as the fast ion conductor additive, so that the DCR can be reduced, the low-temperature discharge performance can be improved, the performance indexes such as high-temperature circulation and the like of the battery are not obviously influenced, and the problem that the conventional lithium ion battery does not haveThe method simultaneously solves the problems of reducing impedance and improving low-temperature discharge performance.

Description

Electrode material, electrode plate, preparation method of electrode plate and lithium ion battery
Technical Field
The invention relates to the field of lithium batteries, in particular to an electrode material, an electrode plate, a preparation method of the electrode plate and a lithium ion battery.
Background
Since the commercialization of lithium ion batteries, lithium ion batteries have been widely used in portable electronic devices due to their advantages such as high energy density and long cycle life, and have been popularized in the fields of electric vehicles and the like. However, the application requirements of various material systems are higher and higher, consumers not only put higher requirements on the energy density and the cycle life of the battery, but also consider the power characteristics and the applicability of the battery in high and low temperature environments. Therefore, the current battery design needs to change ideas and is improved from the aspects of cell design and material systems, so that the requirements of terminal products are met. The direct current impedance (DCR) of the battery is reduced, the dynamic performance of the battery is improved, and the method is an effective way for realizing the high-power characteristic of the battery; the material system is optimized, and the introduction of the rate type negative electrode material and the electrolyte is an effective method for improving the low-temperature environment adaptability and widening the use temperature range of the battery.
At present, the main method for reducing DCR is realized by reducing the particle size, introducing coating modification, optimizing electrolyte and introducing a tab middle-placing or multi-tab technology. Although the method is effective in reducing DCR, the particle size is reduced, the introduction of coating modification and the change of electrolyte generally causes the deterioration of high-temperature performance, and meanwhile, series research needs to be specially carried out on a positive electrode, a negative electrode and the electrolyte, the research and development period is long, and the cost is high. Tab centering and multi-tab technology typically significantly reduces the energy density of the battery. In addition, even if the above method is adopted, if the product requirements of the client and the like cannot be met, other methods are required to further reduce the DCR so as to improve the power characteristics of the battery.
In view of the above, it is necessary to provide a technical solution to the above problems.
Disclosure of Invention
One of the objects of the present invention is: the invention provides an electrode material, which solves the problem that the existing lithium ion battery can not simultaneously reduce the impedance (DCR) and improve the low-temperature discharge performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
an electrode material comprising an active material and a fast ion conductor additive (FIC) which is Li2O-Al2O3-MaOb-SiO2-P2O5Wherein M is Ti and/or Ge, 0<a≤2，0<b≤3。
According to the electrode material provided by the invention, the adopted fast ion conductor additive is a novel compound obtained by various oxides, silicon dioxide is used as a main crystal phase, 4 covalent bonds are formed by 4 valence electrons of silicon atoms and 4 oxygen atoms in the crystal structure, Si atoms are positioned in the center of a regular tetrahedron, O atoms are positioned at the top point of the tetrahedron, the formed atomic crystal framework is stable, other oxides can be easily crystallized, and the obtained novel compound is stable in structure and not easy to collapse. The introduced phosphorus (P) element can reduce the melting point of the oxide, and the microcrystalline formation capability is stronger; the introduced lithium oxide can enhance the compatibility with active material materials on one hand, and provides a lithium source to further enhance the energy density of the battery on the other hand; the introduced alumina has the function of stabilizing crystal lattices, and further promotes the formation of microcrystals under the combined action of the alumina and P; in addition, Ti and/or Ge are introduced into the invention, and both can form a smaller ion channel, and the ion channel has a smaller aperture, so that the crystal structure of the fast ion conductor additive is ensured on one hand, and the aperture of the ion channel is matched with the radius of Li ions on the other hand, so that the ion channel is suitable for migration of the Li ions and can play a role in improving the conductivity of the Li ions.
Preferably, the fast ion conductor additive is Li2O-Al2O3-TiO2-SiO2-P2O5(LATP)、Li2O-Al2O3-GeO2-SiO2-P2O5(LAGP)、Li2O-Al2O3-GeO2-TiO2-SiO2-P2O5(LAGTP).
Preferably, the fast ion conductor additive is made of Li2CO3、Al2O3、MaOb、NH4H2PO4And SiO2And performing crystallization treatment to obtain the product. With Li2CO3、Al2O3、MaOb、NH4H2PO4And SiO2Several substances are used as reaction raw materials, the obtained fast ion conductor additive is simple and efficient to operate and low in price, and the fast ion conductor additive is applied to an electrode material, so that the transmission capability of ions in a pole piece can be effectively enhanced, the fast ion conductor additive also has the advantages of reducing DCR (direct current ratio) and improving low-temperature discharge without influencing high-temperature circulation of the battery, and the overall electrochemical performance of the battery is improved.
Preferably, the mass of the fast ion conductor additive is 0.1-10% of the mass of the electrode material; the particle size of the fast ion conductor additive is 0.05-50 mu m. The DCR is gradually reduced along with the increase of the addition amount of the fast ion conductor additive, but the DCR is not obviously reduced when the addition amount reaches a certain value, which is because the fast ion conductor additive is uniformly dispersed on the electrode under the appropriate addition amount, a relatively perfect ion conducting path is formed, and even if the addition amount of the FIC is further increased, the contribution to further improving the migration rate of lithium ions is small, so that the reduction of the DCR impedance is more facilitated by controlling the addition amount of the fast ion conductor additive within a certain range. However, the grain size of FIC is reduced to some extent, which makes it easier to form a microcrystalline structure, and the ion channel formed by Ti and Ge is more abundant, which can further increase the conductivity of lithium ions, thereby further reducing the DCR value of the lithium ion battery. More preferably, the mass of the fast ion conductor additive is 0.5-5% of the mass of the electrode material; the particle size of the fast ion conductor additive is 0.1-10 mu m.
It is a second object of the present invention to provide an electrode sheet comprising the electrode material described above.
Preferably, the electrode plate is a positive plate, and the active material of the positive plate is at least one of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium-rich manganese base or lithium manganese oxide. Preferably, however, the active material of the electrode of the present invention is mainly lithium cobaltate, which has more excellent properties with fast ion conductors in batteries with high requirements on low temperature and DCR.
The invention also aims to provide a preparation method of the electrode plate, which comprises the following steps:
s1, dispersing the fast ion conductor additive to obtain an additive dispersion liquid;
s2, mixing the adhesive with the additive dispersion liquid to obtain a mixed glue solution;
s3, adding an active substance material and a conductive agent into the mixed glue solution to obtain pole piece slurry;
and S4, coating the pole piece slurry on at least one surface of a current collector, and rolling and cutting to obtain the electrode plate.
The fourth purpose of the invention is to provide another preparation method of the electrode plate, which comprises the following steps:
s1, dry-mixing the active substance material, the conductive agent, the adhesive and the fast ion conductor additive to obtain a powder mixture;
s2, adding the conductive slurry and the organic solvent into the powder mixture, stirring and dispersing to obtain viscous slurry, and adjusting the viscosity to obtain pole piece slurry;
and S3, uniformly coating the pole piece slurry on at least one surface of a current collector, and rolling and cutting to obtain the electrode plate.
The invention also provides a lithium ion battery, which comprises an electrode plate and a diaphragm, wherein the electrode plate is the electrode plate.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the electrode material provided by the invention, the adopted fast ion conductor additive is a novel compound obtained by various oxides, silicon dioxide is used as a main crystal phase, the formed atomic crystal framework is stable, the introduced phosphorus (P) element can reduce the melting point of the oxides, and the microcrystalline formation capability is stronger; the introduced lithium oxide can enhance the compatibility with active material materials on one hand, and provides a lithium source to further enhance the energy density of the battery on the other hand; the introduced alumina has the function of stabilizing crystal lattices, and further promotes the formation of microcrystals under the combined action of the alumina and P; in addition, Ti and/or Ge are introduced into the invention, and both can form a smaller ion channel, and the ion channel has a smaller aperture, so that the crystal structure of the fast ion conductor additive is ensured on one hand, and the aperture of the ion channel is matched with the radius of Li ions on the other hand, so that the ion channel is suitable for migration of the Li ions and can play a role in improving the conductivity of the Li ions. The battery prepared by the electrode material can reduce DCR and improve low-temperature discharge performance, does not significantly influence performance indexes such as high-temperature cycle and the like of the battery, and solves the problem that the conventional lithium ion battery cannot simultaneously reduce impedance and improve low-temperature discharge performance.
2) In addition, the size dimension of the fast ion conductor additive introduced by the electrode material provided by the invention is just between the active substance particles and the conductive agent, and the electrode material and the conductive agent can be well dispersed in gaps among the active substance particles without influencing the compaction performance of a pole piece.
3) In addition, the fast ion conductor additive introduced by the invention also has the advantages of high thermal stability, excellent chemical stability, wide electrochemical window (0-5V) and the like, has good compatibility with other materials on the pole piece such as a current collector and the like, and provides more possibilities for the application of the lithium ion battery in the military fields of mobile phones, notebook computers, digital cameras and other civil electronic products in low-temperature regions, unmanned aerial vehicles and the like.
4) In addition, the electrode plate preparation method provided by the invention has the advantages that the added fast ion conductor additive is not introduced in a form of wrapping the active substance material, so that the fast ion conductor additive can be directly added together with the active substance material during stirring, the operation is simpler and more effective, the preparation can be carried out on the basis of the existing battery manufacturing process without changing, and the method is more suitable for mass production and manufacturing of the current enterprises.
Drawings
FIG. 1 is a comparative graph showing the results of DCR tests of examples 1 to 5 of the present invention and comparative example 1.
FIG. 2 is a graph showing a comparison of EIC test results of examples 1 to 5 of the present invention and comparative example 1.
FIG. 3 is a graph comparing the results of the 20 ℃ low temperature discharge test of examples 1 to 5 of the present invention and comparative example 1.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantages will be described in further detail below with reference to the following detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
An electrode material comprising an active material and a fast ion conductor additive (FIC) which is Li2O-Al2O3-MaOb-SiO2-P2O5Wherein M is Ti and/or Ge, 0<a≤2，0<b≤3。
Further, the fast ion conductor additive is Li2O-Al2O3-TiO2-SiO2-P2O5(LATP)、Li2O-Al2O3-GeO2-SiO2-P2O5(LAGP)、Li2O-Al2O3-GeO2-TiO2-SiO2-P2O5(LAGTP).
Further, the fast ion conductor additive is made of Li2CO3、Al2O3、MaOb、NH4H2PO4And SiO2And performing crystallization treatment to obtain the product. With Li2CO3、Al2O3、MaOb、NH4H2PO4And SiO2Several substances are used as reaction raw materials, the obtained fast ion conductor additive is simple and efficient to operate and low in price, and the fast ion conductor additive is applied to an electrode material, so that the transmission capability of ions in a pole piece can be effectively enhanced, DCR (direct current resistance) is reduced, and low-temperature discharge is improvedThe electricity does not affect the high-temperature circulation of the battery, and the integral electrochemical performance of the battery is improved.
Furthermore, the mass of the fast ion conductor additive is 0.1-10% of that of the electrode material; the particle size of the fast ion conductor additive is 0.05-50 μm. The DCR is gradually reduced along with the increase of the addition amount of the fast ion conductor additive, but the DCR is not obviously reduced when the addition amount reaches a certain value, which is because the fast ion conductor additive is uniformly dispersed on the electrode under the appropriate addition amount, a relatively perfect ion conducting path is formed, and even if the addition amount of the FIC is further increased, the contribution to further improving the migration rate of lithium ions is small, so that the reduction of the DCR impedance is more facilitated by controlling the addition amount of the fast ion conductor additive within a certain range. However, the grain size of FIC is reduced to some extent, which makes it easier to form a microcrystalline structure, and the ion channel formed by Ti and Ge is more abundant, which can further increase the conductivity of lithium ions, thereby further reducing the DCR value of the lithium ion battery. More preferably, the mass of the fast ion conductor additive is 0.5-5% of the mass of the electrode material; the particle size of the fast ion conductor additive is 0.1-10 mu m.
The active material of the positive plate is at least one of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium manganese rich base or lithium manganate, and also can be at least one of lithium iron phosphate, lithium nickelate, lithium nickel cobalt aluminate, lithium nickel manganese oxide, sulfur compound, lithium iron sulfate, lithium fluorophosphate, lithium vanadium fluorophosphate and lithium iron fluorophosphate.
The specific preparation method comprises the following steps:
s1, dissolving the fast ion conductor additive in a solvent according to the mass ratio, and stirring and dispersing to obtain an additive dispersion liquid; wherein the solvent is N-N-dimethyl pyrrolidone (NMP), and the mass ratio of FIC/NMP is 1/100-1/10;
s2, dissolving the adhesive in NMP, adding the additive dispersion liquid, and mixing to obtain a mixed glue solution; the adhesive is polyvinylidene fluoride, the molecular weight is between 50 and 200 ten thousand, and the addition amount is 0.5 to 10 percent;
s3, adding a positive active material lithium cobaltate (4.45V) and a conductive agent into the mixed glue solution to obtain positive plate slurry; the conductive agent comprises at least one of conductive acetylene black, Ketjen black, conductive carbon black (SP), Carbon Nanotubes (CNTs), VGCF and graphene, wherein the SP and the CNTs are adopted in the embodiment, and the addition amount is 0.1-10%; the additive amount of the positive active material is 50-99.5%;
and S4, coating the slurry of the positive plate on two sides of the aluminum foil, rolling and cutting to obtain the positive plate, baking and vacuum drying the positive plate for later use, wherein the specific baking and vacuum drying conditions can refer to the existing setting and are not described herein again.
The second preparation method comprises the following steps:
s1, dry-mixing a positive electrode active material lithium cobaltate (4.45V), conductive carbon black (SP), a polyvinylidene fluoride adhesive and a fast ion conductor additive to obtain a powder mixture;
s2, adding conductive slurry Carbon Nanotubes (CNTs) and an organic solvent (NMP) into the powder mixture, stirring and dispersing with high viscosity to obtain viscous slurry, and adding a proper amount of NMP to adjust the viscosity to obtain anode plate slurry;
and S3, uniformly coating the slurry of the positive plate on two sides of the aluminum foil, rolling and cutting to obtain the positive plate, baking and vacuum drying the positive plate for later use, wherein the specific baking and vacuum drying conditions can refer to the existing setting and are not described herein again.
In the two methods, lithium cobaltate, CNTs, SP and PVDF (polyvinylidene fluoride) are mixed according to the mass ratio of 98.0: 0.5: 0.5: 1.0, stirring and pulping, wherein the mass ratio of the fast ion conductor additive to the lithium cobaltate is 1: 100.
The obtained positive plate is applied to a lithium ion battery, and the lithium ion battery also comprises a negative plate and a diaphragm; the negative plate is prepared by mixing a negative active material, a conductive agent and a binder, and the diaphragm is a ceramic-coated diaphragm.
The preparation method of the negative plate comprises the following steps: negative electrode active material (purchased from jiang violet light in technologies ltd), conductive carbon black (SP), carboxymethyl cellulose (CMC), Styrene Butadiene Rubber (SBR)/acrylic acid (PAA) were mixed in a mass ratio of 95.0: 1.5: 1.5: 2.0, uniformly mixing, and then dispersing in deionized water to obtain cathode plate slurry; and uniformly coating the slurry of the negative plate on two surfaces of the copper foil, rolling and cutting to obtain the negative plate, and finally baking and vacuum drying for later use.
The preparation method of the lithium ion battery comprises the following steps: and sequentially arranging and winding the positive plate, the coated ceramic diaphragm and the negative plate to obtain a bare cell, and carrying out aluminum plastic film packaging, baking, liquid injection, standing, clamp formation, secondary sealing and capacity test to finish the preparation of the lithium ion soft package battery.
According to the above preparation methods, the specific positive electrode material settings of the lithium ion batteries of examples 2 to 22 and comparative examples 1 to 2 are shown in table 1, and the rest are the same as those of example 1, and are not described again.
TABLE 1
Figure BDA0002923566550000081
The lithium ion batteries prepared in the above examples 1 to 22 and comparative examples 1 to 2 were subjected to relevant performance tests including direct current impedance (DCR), Electrochemical Impedance (EIS), low-temperature discharge and high-temperature cycle test, and the specific test methods were as follows:
1. DCR test: charging to 3.8V at constant current and constant voltage of 0.5C, and cutting off the current of 0.02C; ② laying aside for 5 min; ③ 100mA constant current discharge for 10S (100mS sampling point); fourthly, discharging for 1S (100mS sampling point) at a constant current of 1000 mA; fifth, standing for 5 min. DCR ═ 100mA end voltage at 10S discharge-1000 mA end voltage at 1S discharge)/900 mA. The DCR was tested simultaneously at a temperature of 25 deg.C/0 deg.C/10 deg.C above.
2. EIS test: at 25 ℃, a lithium ion battery with 50% SOC is inserted into an electrochemical workstation, and a battery electrochemical impedance analysis spectrum (0.06Hz-100kHz) can be obtained and analyzed and compared.
3. And (3) low-temperature discharge test: firstly, 0.2C partial capacity of the lithium ion battery is divided, 0.05C cutoff current is carried out, and partial capacity C is recorded0. Charging to 4.45V at constant current and constant pressure of 0.5C at normal temperature, and stoppingThe current is stopped at 0.05C. Discharge to 3.0V at 0.2C at various cryogenic temperatures (-20 deg.C/10 deg.C/0 deg.C), record C1. Low temperature discharge ratio ═ C1/C0。
4. High-temperature circulation: under the temperature environment of 45 ℃, the lithium ion battery is charged at 1C/discharged at 1C, the cut-off current is 0.05C, the cycle test is carried out for 500 weeks, and the capacity retention rate of 100 weeks per cycle is recorded.
1. The DCR test results are shown in table 2 and fig. 1.
TABLE 2
Figure BDA0002923566550000091
Figure BDA0002923566550000101
Direct current internal resistance (DCR) is an important index for evaluating the performance of the lithium ion battery, and can reflect the internal polarization condition of the battery in a discharge state, so that the low-temperature performance and the power characteristic of the lithium ion battery are directly influenced. By the method, the DCR under different temperature conditions is particularly tested to know the comprehensive conditions of ohmic internal resistance and internal polarization of the battery core, and then the battery design is optimized according to the size of the DCR so as to meet the application of high-power output products under the low-temperature condition. As can be seen from the comparison of the test data of the above examples and comparative experiments, the DCR of the group to which FIC (fast ion conductor additive) was added was significantly lower than that of the group to which FIC was not added, and the reduction was particularly significant under the low temperature conditions of-10 ℃ and 0 ℃. One is that the difficulty of lithium ion migration is drastically increased due to the decrease in conductivity due to the increase in viscosity of the electrolyte and the vitrification of the negative electrode binder in the battery under low temperature conditions. Secondly, because the FIC has the characteristic of leading lithium ions, the addition of the FIC plays a role in transmitting the lithium ions in the electrode, and is slightly influenced by low temperature.
Furthermore, the comparative data for examples 1-22 show that different types of FIC have different effects on DCR reduction, while different particle sizes and amounts of FIC added have different effects on DCR. The embodiments 1 to 5 are taken as examples for explanation, and the DCR reduction degree of the embodiments 1, 4 and 5 is as follows from large to small: example 1(LATP) > example 4(LAGTP) > example 5 (LAGP). This coincides with the sequential decrease in lithium ion conductivity of LATP, LAGTP, and LAGP materials. The comparative data of example 1 and example 2 demonstrate that reducing the FIC particle size to some extent increases the lithium ion conductivity of the FIC bulk, thereby reducing the DCR value of the lithium ion battery. The comparative data of examples 1 and 3 show that the DCR does not decrease significantly as the FIC addition is increased, which is probably because the FIC is uniformly dispersed on the electrode to form a perfect ion conduction path after 1% of FIC is added, and even if the FIC content is further increased, the FIC content is less contributed to further increase of the lithium ion migration rate, so that the FIC addition of 1% is relatively suitable.
In addition, as can be seen from the comparison of comparative example 2 and example 2, the fast ion conductor additive can improve the resistance of the battery at normal temperature, but cannot effectively improve the resistance of the battery at low temperature, in the electrode material prepared by the conventional coating technique. This is because the fast ion conductor additive of the present invention, when mixed and dispersed with the electrode material, more readily allows Ti and/or Ge to provide an ion channel for insertion into the electrode material. In addition, it can be seen from a comparison of examples 17-22 with examples 1-3 that, when two additives are added, the fast ion conductor additives containing both additives can continue to improve the impedance of-20 ℃ to a small extent with the same addition and particle size, but at 0 ℃ and 25 ℃ with similar contributions to the individual additives.
2. The results of the EIS test are shown in FIG. 2. Wherein only data of examples 1-5 and comparative example 1 are shown in FIG. 2 for comparison, and it can be seen from EIS chart that the ohmic resistance Rs of the batteries of examples 1-5 and comparative example are close, and the magnitude of the electrochemical transfer resistance Rct is basically consistent with the order of magnitude of DCR: example 2 < example 3 < example 1 ≈ example 4 ≈ example 5 < comparative example 1.
3. The results of the low temperature discharge test are shown in table 3 and fig. 3.
TABLE 3
Figure BDA0002923566550000111
Figure BDA0002923566550000121
From the above test results, it can be seen that due to the addition of FIC, the low-temperature discharge ratio of the lithium ion battery at-20 ℃, -10 ℃ and 0 ℃ is significantly increased, and when the addition type of FIC and the particle size and the addition amount thereof are controlled, the low-temperature discharge performance of the lithium ion battery can be more excellent, for example, the increase of example 2 (1% 0.5 μm LATP) at-20 ℃ can be 12.8%. Taking examples 1-5 as examples, the low-temperature discharge ratio is as follows from high to low: example 2 > example 3 > example 1 > example 4 > example 5 > comparative example 1. This is because, under low temperature conditions, the mobility difficulty of lithium ions is drastically increased due to the decrease in conductivity due to the increase in viscosity of the electrolyte and the vitrification of the negative electrode binder in the battery, but FIC itself has a property of conducting lithium ions, and the addition of FIC plays a role of transporting lithium ions in the electrode and is little affected by low temperature environments. The data results of the low temperature discharge and the data of the low temperature DCR are matched with each other.
From the results of the DCR test and the low-temperature discharge test, it can be seen that the addition of FIC has an obvious effect on the reduction of DCR and the improvement of low-temperature discharge performance, but the effect achieved by the existing methods such as an electrolyte, an adhesive, an active material and the like generally affects high-temperature indexes such as high-temperature cycle of the battery remarkably, so that the high-temperature cycle performance of the lithium ion batteries of examples 1 to 22 and comparative examples 1 to 2 at 45 ℃ is continuously tested.
4. The results of the high temperature cycling are shown in Table 4.
TABLE 4
Figure BDA0002923566550000131
From the above experimental results, the 500-week capacity retention rate of the embodiment of the present invention added with FIC is not different from that of the comparative example 1, showing that the high-temperature cycle performance is not deteriorated by adding FIC; however, from the experimental result of comparative example 2, the capacity of the lithium ion battery is reduced after long-time circulation by using the electrode material obtained by wrapping the active material with the fast ion conductor additive of the present invention, and the result further proves that the fast ion conductor additive of the present invention is more suitable for being prepared by doping and embedding the active material, and the ion channel obtained by the method can maintain good low-temperature performance at low temperature and maintain the capacity retention rate of the conventional battery at high temperature, thereby avoiding the problem that the high-temperature performance is deteriorated when the DCR is reduced by the existing method.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (10)

1. An electrode material, which is characterized by comprising an active material and a fast ion conductor additive, wherein the fast ion conductor additive is Li2O-Al2O3-MaOb-SiO2-P2O5Wherein M is Ti and/or Ge, 0<a≤2，0<b≤3。
2. The electrode material of claim 1, wherein the fast ion conductor additive is Li2O-Al2O3-TiO2-SiO2-P2O5、Li2O-Al2O3-GeO2-SiO2-P2O5、Li2O-Al2O3-GeO2-TiO2-SiO2-P2O5At least one of (1).
3. The electrode material of claim 1 or 2, wherein the fast ion conductor additive is made from Li2CO3、Al2O3、MaOb、NH4H2PO4And SiO2And performing crystallization treatment to obtain the product.
4. The electrode material of claim 1, wherein the mass of the fast ion conductor additive is 0.1-10% of the mass of the electrode material; the particle size of the fast ion conductor additive is 0.05-50 mu m.
5. The electrode material of claim 4, wherein the mass of the fast ion conductor additive is 0.5-5% of the mass of the electrode material.
6. An electrode sheet comprising the electrode material according to any one of claims 1 to 5.
7. The electrode sheet according to claim 6, wherein the electrode sheet is a positive electrode sheet, and the active material of the positive electrode sheet is at least one of lithium cobaltate, lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium rich manganese base, or lithium manganese oxide.
8. The preparation method of the electrode plate is characterized by comprising the following steps:
s1, dispersing the fast ion conductor additive to obtain an additive dispersion liquid;
s2, mixing the adhesive with the additive dispersion liquid to obtain a mixed glue solution;
s3, adding an active substance material and a conductive agent into the mixed glue solution to obtain pole piece slurry;
and S4, coating the pole piece slurry on at least one surface of a current collector, and rolling and cutting to obtain the electrode plate.
9. The preparation method of the electrode plate is characterized by comprising the following steps:
s1, dry-mixing the active substance material, the conductive agent, the adhesive and the fast ion conductor additive to obtain a powder mixture;
s2, adding the conductive slurry and the organic solvent into the powder mixture, stirring and dispersing to obtain viscous slurry, and adjusting the viscosity to obtain pole piece slurry;
and S3, uniformly coating the pole piece slurry on at least one surface of a current collector, and rolling and cutting to obtain the electrode plate.
10. A lithium ion battery comprising an electrode sheet and a separator, wherein the electrode sheet is the electrode sheet according to claim 6 or 7.
CN202110126075.4A 2021-01-29 2021-01-29 Electrode material, electrode plate, preparation method of electrode plate and lithium ion battery Pending CN112786891A (en)

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