阅读说明：本技术 测试电极材料安全性能的方法 (Method for testing safety performance of electrode material ) 是由 刘子佳 姜艳 于 2019-10-23 设计创作，主要内容包括：本发明提供了一种测试电极材料安全性能的方法。该方法包括：(1)将电极材料、导电材料和粘结剂混合后涂布于集流体上,以便得到电极片；(2)利用所述电极片装配电池,对所述电池进行充放电循环后再充至满电状态；(3)对所述满电状态的电池进行拆解,以便取出所述电极片；(4)将电解液和步骤(3)得到的电极片转移至坩埚中密封后置于示差扫描量热仪中进行测试,以便得到所述电极材料的安全性能。该方法不仅简单便捷,而且可重复性高,测试结果准确、可靠,每个样品测试结果的准确率误差不高于1％。(The invention provides a method for testing the safety performance of an electrode material. The method comprises the following steps: (1) mixing an electrode material, a conductive material and a binder, and coating the mixture on a current collector to obtain an electrode plate; (2) assembling a battery by using the electrode plate, and carrying out charge-discharge circulation on the battery and then recharging the battery to a full charge state; (3) disassembling the battery in the full-charge state so as to take out the electrode plate; (4) and (4) transferring the electrolyte and the electrode plate obtained in the step (3) into a crucible, sealing, and then placing into a differential scanning calorimeter for testing so as to obtain the safety performance of the electrode material. The method is simple, convenient and fast, high in repeatability, accurate and reliable in test result, and the error of the accuracy of the test result of each sample is not higher than 1%.)

1. A method for testing the safety performance of an electrode material, comprising:

(1) mixing an electrode material, a conductive material and a binder, and coating the mixture on a current collector to obtain an electrode plate;

(2) assembling a battery by using the electrode plate, and carrying out charge-discharge circulation on the battery and then recharging the battery to a full charge state;

(3) disassembling the battery in the full-charge state so as to take out the electrode plate;

(4) and (4) transferring the electrolyte and the electrode plate obtained in the step (3) into a crucible, sealing, and then placing into a differential scanning calorimeter for testing so as to obtain the safety performance of the electrode material.

2. The method according to claim 1, wherein in the step (1), the electrode material is a positive electrode material, and the electrode sheet is a positive electrode sheet.

3. The method according to claim 1 or 2, wherein in the step (1), the mass ratio of the electrode material, the conductive material and the binder is (80-95): (1-10): (1-10) of a first step,

optionally, in the step (1), the solid content of the slurry formed by mixing the electrode material, the conductive material and the binder is 50-65 wt%.

4. The method according to claim 3, wherein in step (1), the electrode material and the conductive material are subjected to a first vacuum drying treatment in advance before the mixing,

optionally, the temperature of the first vacuum drying treatment is 150-180 ℃, and the heat preservation time is 6-10 h.

5. The method according to claim 1 or 4, wherein in the step (2), the battery is charged to a full charge state after 2-5 charge-discharge cycles with a current of 0.1-0.2C rate,

optionally, the charge cut-off voltage of the battery is 4.3V, the discharge cut-off voltage is 3.0V, and the voltage in a full-charge state is 4.25-4.3V,

optionally, in step (2), the electrolyte used to assemble the battery includes lithium salt, ethylene carbonate, ethyl methyl carbonate, and dimethyl carbonate.

6. The method according to claim 5, characterized in that the electrode sheet is subjected to a first cutting and/or a second vacuum drying process in advance before the step (2),

optionally, the temperature of the second vacuum drying treatment is 100-130 ℃, and the heat preservation time is 6-10 h.

7. The method of claim 1 or 6, wherein step (3) further comprises: cleaning and second cutting the electrode sheet which is disassembled and taken out,

optionally, the washing is performed with an organic solvent used to formulate the battery electrolyte,

optionally, the organic solvent is at least one selected from the group consisting of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate, preferably dimethyl carbonate.

8. The method of claim 7, wherein steps (2) and (3) are performed in a glove box having an inert atmosphere therein and having a moisture content and an oxygen content of no more than 0.1 ppm.

9. The method according to claim 1 or 8, wherein in the step (4), the solid-to-liquid ratio of the electrode sheet to the electrolyte is (5-10) mg/1 μ L, the electrolyte has the same composition as the electrolyte used for assembling the battery,

optionally, in the step (4), the temperature range of the test is 25-300 ℃, the heating rate is (5-10) K/min,

optionally, in the step (4), the crucible is internally protected by inert gas, and the gas flow rate of the inert gas is 30-50 m L/min.

10. The method of claim 9, comprising:

(i) carrying out first vacuum drying treatment on the positive electrode material and the conductive material;

(ii) (ii) mixing the electrode material obtained in the step (i), the conductive material and a binder to form slurry, coating the slurry on the current collector, and drying to obtain a positive plate;

(iii) carrying out first cutting and/or second vacuum drying treatment on the positive plate;

(iv) (iv) assembling a battery by using the positive plate obtained in the step (iii) and combining a metal lithium plate as a negative electrode, and preparing an electrolyte by using lithium salt, ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, and charging and discharging the battery for circulation and then recharging the battery to a full charge state;

(v) disassembling the battery in the full-charge state, taking out the positive plate, cleaning the positive plate by using dimethyl carbonate, and then performing second cutting;

(vi) and (5) transferring the positive plate obtained in the step (v) and the electrolyte prepared in the step (iv) into a high-pressure crucible, sealing, and then placing into a differential scanning calorimeter for testing so as to obtain the safety performance of the positive material.

Technical Field

The invention relates to the technical field of lithium batteries, in particular to a method for testing the safety performance of an electrode material.

Background

With the increasingly prominent problems of energy crisis, environmental pollution and the like, the development of sustainable new energy becomes urgent for building a low-carbon society. Lithium ion batteries are receiving much attention as a new type of high-energy green batteries. The lithium battery has the advantages of high voltage and high capacity, and has long cycle life, low cost, etc. However, the anode material has a higher price and a lower specific capacity, which makes the lithium ion battery a bottleneck in large-scale popularization and application, and compared with the cathode material, the anode material has a lower energy density and a lower power density, and is also a main cause of the safety hazard of the power lithium ion battery. Although the protection circuit of the lithium battery is mature, the selection of the anode material is critical to ensure the safety of the battery.

At present, differential scanning calorimetry is mainly adopted for evaluating the safety and the thermal stability of the lithium ion battery cathode material, and two methods are mainly adopted: one is that the battery in a charging state is disassembled and then the anode is taken out, the excessive electrolyte on the surface of the electrode is removed, the anode material is scraped from the current collector, and a proper amount of the anode material is put into a stainless steel sealed crucible for DSC test; and the other is that a button half cell is prepared by several anode materials of the same type, the button half cell is charged to a full state after cyclic activation, the half cell is disassembled, and the anode plate scraping powder and the electrolyte are subjected to DSC test together. However, scraping the positive electrode material and the powder on the pole piece on the current collector wastes manpower and material resources as well as resources, and if the scraping method is improper, batteries made of the same material can be repeatedly manufactured, and each battery needs to be recharged; in addition, if the electrolyte is not completely removed, the test result is bimodal, and the test result is inaccurate.

Therefore, methods for evaluating the safety and thermal stability of the lithium ion battery positive electrode material have yet to be further improved.

Disclosure of Invention

In view of this, the present invention is directed to a method for testing safety performance of an electrode material, so as to improve repeatability of testing and accuracy of a testing result. In order to achieve the purpose, the technical scheme of the invention is realized as follows:

the invention provides a method for testing the safety performance of an electrode material, which comprises the following steps of:

(1) mixing an electrode material, a conductive material and a binder, and coating the mixture on a current collector to obtain an electrode plate;

(2) assembling a battery by using the electrode plate, and carrying out charge-discharge circulation on the battery and then recharging the battery to a full charge state;

(3) disassembling the battery in the full-charge state so as to take out the electrode plate;

(4) and (4) transferring the electrolyte and the electrode plate obtained in the step (3) into a crucible, sealing, and then placing into a differential scanning calorimeter for testing so as to obtain the safety performance of the electrode material.

Further, in the step (1), the electrode material is a positive electrode material, and the electrode sheet is a positive electrode sheet.

Further, in the step (1), the mass ratio of the electrode material, the conductive material and the binder is (80-95): (1-10): (1-10).

Further, the solid content of slurry formed by mixing the electrode material, the conductive material and the binder is 50-65 wt%.

Further, in the step (1), the electrode material and the conductive material are subjected to a first vacuum drying treatment in advance before the mixing.

Further, the temperature of the first vacuum drying treatment is 150-180 ℃, and the heat preservation time is 6-10 hours.

Further, in the step (2), the battery is charged to a full charge state after 2-5 charge-discharge cycles by adopting current with 0.1-0.2C multiplying power.

Furthermore, the charging cut-off voltage of the battery is 4.3V, the discharging cut-off voltage is 3.0V, and the voltage of a full-charge state is 4.25-4.3V.

Further, in the step (2), the electrolyte used for assembling the battery includes lithium salt, ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate.

Further, the electrode sheet is subjected to a first cutting and/or a second vacuum drying treatment in advance before the step (2) is performed.

Further, the temperature of the second vacuum drying treatment is 100-130 ℃, and the heat preservation time is 6-10 hours. Further, the step (3) further comprises: and cleaning and second cutting the electrode slice which is disassembled and taken out.

Further, the washing is performed using an organic solvent used for preparing the battery electrolyte.

Further, the organic solvent is at least one selected from the group consisting of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate, preferably dimethyl carbonate.

Further, the step (2) and the step (3) are carried out in a glove box, wherein the inside of the glove box is in an inert gas environment, and the water content and the oxygen content are not higher than 0.1 ppm.

Further, in the step (4), the solid-to-liquid ratio of the electrode plate to the electrolyte is (5-10) mg/1 mu L, and the composition of the electrolyte is the same as that of the electrolyte used for assembling the battery.

Further, in the step (4), the temperature range of the test is 25-300 ℃, and the heating rate is (5-10) K/min.

Further, in the step (4), the crucible is protected by inert gas, and the gas velocity of the inert gas is 30-50 m L/min.

Further, the method for testing the safety performance of the electrode material comprises the following steps: (i) carrying out first vacuum drying treatment on the positive electrode material and the conductive material; (ii) (ii) mixing the electrode material obtained in the step (i), the conductive material and a binder to form slurry, coating the slurry on the current collector, and drying to obtain the positive plate; (iii) carrying out first cutting and/or second vacuum drying treatment on the positive plate; (iv) (iv) assembling a battery by using the positive plate obtained in the step (iii) and combining a metal lithium plate as a negative electrode, and preparing an electrolyte by using lithium salt, ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, and charging and discharging the battery for circulation and then recharging the battery to a full charge state; (v) disassembling the battery in the full-charge state, taking out the positive plate, cleaning the positive plate by using dimethyl carbonate, and then performing second cutting; (vi) and (5) transferring the positive plate obtained in the step (v) and the electrolyte prepared in the step (iv) into a high-pressure crucible, sealing, and then placing into a differential scanning calorimeter for testing so as to obtain the safety performance of the positive material.

Compared with the prior art, the method for testing the safety performance of the electrode material has at least the following advantages: on one hand, the testing method does not need to scrape powder on the current collector or the pole piece, so that manpower, material resources and resources are saved, the battery made of the same material is not required to be repeatedly manufactured and recharged, and the problem of inaccurate testing result caused by double peaks in the testing result can be avoided; on the other hand, the testing method provided by the invention can better simulate the full battery environment by cutting the activated positive plate and then directly mixing the cut positive plate with the electrolyte for DSC testing, thereby further improving the accuracy of the testing result. In conclusion, the method is simple, convenient and fast, high in repeatability, accurate and reliable in test result, and the error of the accuracy of the test result of each sample is not higher than 1%.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:

fig. 1 is a flowchart of a method for testing safety performance of an electrode material according to an embodiment of the present invention.

FIG. 2 is a DSC chart of example 1 of the present invention tested twice at the same level.

FIG. 3 is a DSC chart of comparative example 1 according to the present invention, which was tested twice at the same level.

FIG. 4 is a DSC graph of comparative example 2 according to the present invention, which was tested twice at the same level.

FIG. 5 is a DSC chart of example 2 of the present invention tested twice at the same level.

FIG. 6 is a DSC chart of example 3 of the present invention tested twice at the same level.

Detailed Description

It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.

According to one aspect of the invention, a method for testing the safety performance of an electrode material is provided. According to an embodiment of the invention, the method comprises: (1) mixing an electrode material, a conductive material and a binder, and coating the mixture on a current collector to obtain an electrode plate; (2) assembling a battery by using an electrode plate, and carrying out charge-discharge circulation on the battery and then recharging the battery to a full charge state; (3) disassembling the battery in a full-charge state so as to take out an electrode plate; (4) and (4) transferring the electrolyte and the electrode plate obtained in the step (3) into a crucible, sealing, and then placing into a differential scanning calorimeter for testing so as to obtain the safety performance of the electrode material. The method is simple, convenient and fast, high in repeatability, accurate and reliable in test result, and the error of the accuracy of the test result of each sample is not higher than 1%.

The invention will be described in more detail below with reference to the accompanying figure 1 and with reference to an embodiment.

S100, mixing the electrode material, the conductive material and the binder, and coating the mixture on a current collector to obtain an electrode plate

According to a specific embodiment of the present invention, the types of the electrode material, the conductive material and the binder in the present invention are not particularly limited, and those skilled in the art can select the electrode material according to actual needs, for example, the electrode material may be a positive electrode material/a negative electrode material, in which case the electrode sheet corresponds to a positive electrode sheet/a negative electrode sheet, wherein the positive electrode material may be a nickel-cobalt-manganese ternary positive electrode material, a nickel-cobalt-aluminum positive electrode material, and a positive electrode material such as lithium manganate or lithium iron phosphate, the conductive material may be conductive carbon black, conductive graphite, and the binder may be polyvinylidene fluoride (PVDF), and the like. In addition, the binder can be dissolved in an organic solvent and then mixed with the electrode material and the conductive material, so that the uniform mixing of the materials is facilitated, the uniformity and the stability of the slurry are improved, and the solid content of the slurry formed after mixing is controlled.

According to still another embodiment of the present invention, the electrode material may be a positive electrode material, and the electrode tab may be a positive electrode tab, whereby the safety and thermal stability of the battery positive electrode material may be conveniently and accurately evaluated.

According to another embodiment of the invention, the mass ratio of the electrode material, the conductive material and the binder can be (80-95): (1-10): (1-10), by controlling the mass ratio, the adhesion between the electrode material and the current collector can be remarkably increased, the electrode plate is ensured to have better conductivity, the thickness of an active material layer in the electrode plate can be remarkably increased, and the energy density and the cycle life of the prepared lithium battery are remarkably improved.

According to another embodiment of the invention, the solid content of the slurry formed by mixing the electrode material, the conductive material and the binder can be 50-65 wt%, so that the defects that the electrode sheet has particles or an active material layer is not uniform due to uneven coating of the slurry on the current collector can be effectively avoided.

According to another embodiment of the present invention, the first vacuum drying process may be performed on the electrode material and the conductive material in advance before the mixing, so that negative effects of moisture and air remaining in the electrode material and the conductive material on the battery performance may be effectively avoided, thereby further improving the stability of the battery and the accuracy of the test result. Further, the temperature of the first vacuum drying treatment can be 150-180 ℃, and the heat preservation time can be 6-10 hours, so that the drying effect can be ensured, and the problem that the conductive material, the binder and the like are failed due to reaction or structural change caused by overhigh temperature can be avoided.

S200, assembling the battery by using the electrode plate, and charging and discharging the battery to a full charge state after the battery is charged and discharged circularly

According to a specific embodiment of the invention, the battery can be charged to a full charge state after being subjected to charge-discharge cycles for 2-5 times by adopting a current with a rate of 0.1-0.2C, and the inventor finds that if the current rate during charge-discharge treatment is too large, the phenomenon of insufficient charge or insufficient discharge of the battery is easily caused, and the normal charge-discharge and full charge states of the battery can be ensured by adopting the current with the rate of 0.1-0.2C for charge-discharge in the invention, so that the electrode plate is fully activated; in addition, the inventor also finds that the capacity retention rate of the battery is reduced along with the increase of the number of charge-discharge cycles, and the invention can ensure that the electrode plates can be fully activated and the battery can be fully charged before being disassembled by controlling the charge-discharge cycles to be 2-5 times.

According to still another embodiment of the present invention, the specification of the battery when assembling the battery in the present invention is not particularly limited, and those skilled in the art can select the battery according to actual needs. The battery specifications are different, and the cut-off voltage for charging and discharging the battery is also different, for example, the battery may be a button battery, the cut-off voltage for charging the battery may be 4.3V, the cut-off voltage for discharging the battery may be 3.0V, and the voltage when the battery reaches a full-charge state may be 4.25 to 4.3V.

According to still another embodiment of the present invention, the electrolyte for assembling the battery may include lithium salt, Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), and dimethyl carbonate (DMC), wherein the kind of the lithium salt and the volume ratio of the ethylene carbonate, the ethyl methyl carbonate, and the dimethyl carbonate are not particularly limited and may be selected by those skilled in the art according to actual needs, for example, the lithium salt may be L iPF₆And the ratio of the ethylene carbonate, the ethyl methyl carbonate and the dimethyl carbonate can be 2:4:4, and the concentration of the lithium salt in the electrolyte can be 1.05-1.2 mol/L, so that the electrode plate can be fully activated, and the normal lithium removal of the cathode material is ensured.

According to another embodiment of the present invention, the electrode tabs may be subjected to a first cutting and/or a second vacuum drying process in advance before the battery is assembled, wherein the electrode tabs may be cut according to the specification and model of the target battery, thereby not only facilitating the assembly of the battery, but also effectively avoiding negative effects of moisture and air remaining on the electrode tabs on the battery performance, thereby further improving the stability of the battery and the accuracy of the test result.

According to a specific example of the present invention, when the target battery is a button cell battery, such as a 2032 button cell battery, the electrode tabs can be cut into circular electrode tabs with a diameter of 10-14 mm. In addition, the temperature of the second vacuum drying treatment can be 100-130 ℃, and the heat preservation time can be 6-10 hours, so that the drying effect can be ensured, and the problem that the conducting materials, the binding agents and the like on the electrode plates are invalid due to reaction or structural change caused by overhigh temperature can be avoided.

According to another embodiment of the present invention, the battery assembly can be performed in a glove box, which can be an inert gas environment, and the water content and the oxygen content are not higher than 0.1ppm, so that the stability of the battery and the accuracy of the test result can be further improved.

S300, disassembling the battery in the full-charge state, and taking out electrode plates

According to a specific embodiment of the invention, the electrode plate which is disassembled and taken out can be cleaned and cut for the second time, so that the electrolyte remained on the electrode plate can be effectively removed, the electrode plate can be completely soaked by the electrolyte in the subsequent testing process, the full-battery environment can be better simulated in the subsequent testing process, and the accuracy of the testing result can be further improved.

According to still another embodiment of the present invention, the washing may be performed using an organic solvent used for preparing the electrolyte of the battery, for example, when the electrolyte is composed of a lithium salt, ethylene carbonate, ethyl methyl carbonate, and dimethyl carbonate, the organic solvent may be at least one selected from the group consisting of ethylene carbonate, ethyl methyl carbonate, and dimethyl carbonate, preferably dimethyl carbonate. Therefore, the active material layer on the electrode plate can be effectively prevented from falling off or other side reactions with the active material layer on the electrode plate caused by other organic solvents, and the accuracy and the reliability of the test structure are ensured.

According to another embodiment of the invention, the disassembling of the battery and the cleaning and cutting of the electrode plates can be performed in a glove box, the glove box can be in an inert gas environment, and the water content and the oxygen content are not higher than 0.1ppm, so that the accuracy of the subsequent test result can be further ensured.

S400, transferring the electrolyte and the electrode slice obtained in the step S300 into a crucible, sealing, and then placing the crucible into a differential scanning calorimeter for testing to obtain the safety performance of the electrode material

According to an embodiment of the invention, the solid-to-liquid ratio of the electrode plate to the electrolyte can be (5-10) mg/1 mu L, and the composition of the electrolyte is the same as that of the electrolyte adopted by the assembled battery.

According to another embodiment of the invention, the temperature range during the test can be 25-300 ℃, the temperature rise rate can be (5-10) K/min, and the inventor finds that the thermal decomposition temperature of the common anode material is usually below 300 ℃, for example, the ternary anode material NCM811 can be thermally decomposed to release oxygen between 200 ℃ and 230 ℃, so as to obtain the test result.

According to another embodiment of the invention, during testing, the crucible can be protected by inert gas, and the gas flow rate of the inert gas can be 30-50 m L/min, so that the reaction environment in the full cell can be better simulated, and the accuracy and reliability of the detection result can be further improved.

According to a specific embodiment of the present invention, a method for testing safety performance of an electrode material may include: (i) carrying out first vacuum drying treatment on the positive electrode material and the conductive material; (ii) (ii) mixing the electrode material obtained in the step (i), a conductive material and a binder to form slurry, coating the slurry on a current collector, and drying to obtain a positive plate; (iii) carrying out first cutting and/or second vacuum drying treatment on the positive plate; (iv) (iv) using the positive plate obtained in the step (iii) and combining a metal lithium plate as a negative electrode, preparing an electrolyte by using lithium salt, ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate to assemble a battery, and charging and discharging the battery for circulation and then recharging the battery to a full charge state; (v) disassembling the battery in the full-charge state, taking out the positive plate, cleaning the positive plate by using dimethyl carbonate, and then performing second cutting; (vi) and (5) transferring the positive plate obtained in the step (v) and the electrolyte prepared in the step (iv) into a high-pressure crucible, sealing, and then placing into a differential scanning calorimeter for testing so as to obtain the safety performance of the positive material. Therefore, the accuracy and the reliability of the detection result can be further improved.

Compared with the prior art, the electrode material safety performance testing method has at least the following advantages: on one hand, the testing method does not need to scrape powder on the current collector or the pole piece, so that manpower, material resources and resources are saved, the battery made of the same material is not required to be repeatedly manufactured and recharged, and the problem that the testing result is inaccurate due to the fact that the testing result has double peaks is solved; on the other hand, the testing method provided by the invention can better simulate the full battery environment by cutting the activated positive plate and then directly mixing the cut positive plate with the electrolyte for DSC testing, thereby further improving the accuracy of the testing result. In conclusion, the method is simple, convenient and fast, high in repeatability, accurate and reliable in test result, and the error of the accuracy of the test result of each sample is not higher than 1%.

The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.