CN108155347B - Method for improving first coulomb efficiency of nickel-containing anode material of lithium ion battery and application thereof - Google Patents
Method for improving first coulomb efficiency of nickel-containing anode material of lithium ion battery and application thereof Download PDFInfo
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Abstract
The invention relates to a method for improving the first coulomb efficiency of a nickel-containing anode material of a lithium ion battery and application thereof, wherein lithium ions in a nickel-containing anode plate are partially removed in advance in a charging and discharging mode, the first charging gram capacity of the nickel-containing anode material is adjusted in a partial lithium ion removing mode, and the first reversible discharging gram capacity of the anode material is not reduced, so that the first efficiency of the nickel-containing anode material of the lithium ion battery is improved; when the full battery is designed, the initial coulomb efficiency of the anode material in the lithium ion full battery is the same as the initial coulomb efficiency of the corresponding cathode material, so that the excessive amplitude of the cathode material is reduced, and the energy density of the full battery is improved. Has the advantages that: according to the method, lithium ions in the nickel-containing positive plate are removed in advance in a charging and discharging mode, so that the initial coulomb efficiency of the positive material is improved, the initial coulomb efficiency of the nickel-containing positive material can be adjusted as required, and the initial efficiency matching of the nickel-containing positive material and the negative material in the design of the full cell is optimal.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a method for improving the initial coulomb efficiency of a nickel-containing anode material of a lithium ion battery and application thereof.
Background
The positive electrode material adopted by the lithium ion battery is one of key materials for manufacturing the lithium ion battery, and occupies a core position in the lithium ion battery. Currently, the anode materials which are industrially applied mainly comprise lithium cobaltate, lithium manganate, ternary lithium nickel cobalt manganese oxide materials and lithium iron phosphate. The nickel cobalt lithium manganate and nickel cobalt lithium aluminate ternary material has the advantages of high electrochemical capacity, good cycle performance, easy synthesis, low raw material cost and the like, gradually replaces part of lithium cobaltate in recent years, and enters the market of small lithium battery anode materials. In addition, the lithium nickel cobalt manganese oxide nickel cobalt aluminate lithium nickel cobalt has high weight specific capacity and high weight energy density, is favorable for improving the weight energy density of the power lithium ion battery, and is also applied to the field of small and medium-sized lithium ion power batteries.
When preparing the positive electrode material containing Ni, Ni is used2+Is difficult to be completely oxidized into Ni3+Thus prepared Ni-containing3+The positive electrode material (2) usually contains a certain amount of Ni2+. Due to Ni2+Diameter and Li+The radii are very close, so Ni is in the material2+Possibly occupying Li+Position, and Li+May occupy Ni2+This is the cation-trapping phenomenon between Li and Ni. After the mixed-discharging between the transition metal ions and the lithium ions occurs, the movement of the lithium ions is obstructed by the transition metal ions, so the mixed-discharging of the cations causes the reduction of the electrochemical performance of the material in the aspects of reversible capacity, first efficiency and the like. In the first charge formation process of the battery made of the nickel-containing cathode material, lithium ions are extracted from the layered structure of the cathode and are embedded into the cathode, and Ni is added at the moment2+Will occupy Li in the lithium layer+The transmission of the position ions causes obstruction, so that a part of lithium ions can not be smoothly inserted into the crystal lattice of the anode material in the discharging process. Since the reversible capacity of the material is realized by reversible intercalation and deintercalation of lithium ions in the crystal lattice of the positive electrode, and the Li/Ni mixed-exclusion can cause the reversible intercalation and deintercalation quantity of the lithium ions to be reduced, the Li/Ni mixed-exclusion can reduce the first coulombic efficiency of the material. Meanwhile, during the first charge, Li in the lithium layer and the transition metal layer+Can be removed. However, during the first discharge, a part of lithium can not return to the crystal lattice of the transition metal layer, so that the first coulombic efficiency of the material is further reduced.
Currently, the mainstream nickel-containing anode material in the market, such as nickel-cobalt lithium aluminate (NCA) and nickel-cobalt lithium manganate (including NCM111, NCM523, NCM622, NCM811 and the like), has a coulombic efficiency of 82% -90% in the first charge and discharge of a button half cell of a lithium sheet, and the mainstream cathode material, such as natural graphite, mesocarbon microbeads and the like, has a coulombic efficiency of 91.5% -94% in the first charge and discharge of the lithium half cell, so that when the cathode of the current mainstream graphite carbon material is matched with the cathode of the current cathode of the button half cell, the gram capacities of the anode and the cathode are balanced according to the gram capacity of the first charge of the nickel-containing anode material in the lithium button half cell and the gram capacity of the cathode in the lithium button half cell, and the first coulombic efficiency of the designed full cell is controlled by the nickel-containing anode material with lower first coulombic efficiency in the anode and the cathode, the first coulomb efficiency of the nickel-containing anode material is improved, and then the first efficiency of the full cell can be improved.
At present, the first efficiency of improving the nickel-containing ternary material is mainly optimized in the material synthesis process. For example, as the content of Ni in reactants is increased in the synthesis process, the cation mixing degree is increased, and the impedance of the material is increased, and conversely, as the content of Li in the reactants is increased, the order degree of Li and Ni is increased, and the impedance is reduced, so that the occurrence of cation mixing can be reduced by adding excessive lithium in the synthesis process, but the introduction of excessive lithium can cause the alkalinity of the synthesized positive electrode material to be increased, influence the processability and stability in the material homogenizing and coating process, and increase the gas production in the formation process; in addition, Li can be reduced by lowering the firing temperature during the material synthesis+Vacancy, suppression of Ni2+The temperature is reduced, so that crystal grains are difficult to grow up, more closed holes are formed, and the improvement on the compaction density of the material is not favorable; the Ni can be inhibited by doping Mg, Al and other elements in the synthesis process2+But the doping of the metal element will sacrifice the gram capacity of the material, causing adverse effects. The lithium battery manufacturing industry needs to solve the bottleneck problem of improving the first coulomb efficiency of the nickel-containing anode material of the lithium ion battery.
Disclosure of Invention
The invention aims to overcome the defects of the technology and provides a method for improving the first coulomb efficiency of a nickel-containing anode material of a lithium ion battery and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: a method for improving the initial coulomb efficiency of a nickel-containing anode material of a lithium ion battery is characterized in that: lithium ions in the nickel-containing positive plate are partially extracted in advance in a charging and discharging mode, the first charging gram capacity of the nickel-containing positive material is adjusted in the partial lithium ion extracting mode, and the first reversible discharging gram capacity of the positive material is not reduced, so that the first efficiency of the nickel-containing positive material of the lithium ion battery is improved;
the method comprises the following specific steps:
firstly, placing a positive plate coated with a nickel-containing positive material on a current collector and a counter electrode serving as a lithium carrier in the electrolyte of the lithium ion battery together to form the lithium ion battery;
secondly, connecting a positive terminal of an external power supply with the current collector containing the nickel positive material in the step one, and connecting a negative terminal of the external power supply with the lithium carrier in the step one;
thirdly, the lithium ion battery in the step one is charged and activated by the external power supply in the step two, and lithium ions enter the counter electrode in the step one; discharging the charged lithium ion battery, and returning lithium ions to the nickel-containing positive electrode material on the positive electrode plate in the step (I);
the nickel-containing positive electrode material includes, but is not limited to, lithium nickelate, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminate; counter electrodes as lithium carriers include, but are not limited to, lithium foil, graphitic carbon anodes, silicon anodes, or silicon oxide anodes.
The counter electrode used as the lithium carrier adopts a metal lithium sheet or a lithium foil.
An isolating membrane is arranged between the positive plate and the counter electrode, the isolating layer is a PP or PE film, and preferably, the porosity of the PP or PE film is 20% -60%.
The external power supply controls the current and voltage applied between the positive plate and the counter electrode, and preferably, a power supply having constant current, constant voltage, and capacity calculation functions is used.
The amount of lithium ions removed from the positive electrode material in the charging and activating process of the external power supply is adjusted between 0 and 100 percent, and one charge capacity of the nickel-containing positive electrode material is 100 percent; the amount of lithium ions returning to the cathode material during the discharging process is adjusted between 0 and 100 percent, the amount of lithium ions removed from the cathode material during the charging activation process is 100 percent, and the charging current during the charging process is between 0.01 and 2C, preferably between 0.05 and 0.15C; the discharge current is between 0.01C-2C, preferably between 0.05C-0.15C.
The theoretical first effect calculation method of the positive plate after the treatment of the steps (I) to (III) comprises the following steps:
1) the one-gram charge capacity of the positive electrode material on the treated nickel-containing positive electrode plate is less than the first reversible gram capacity before treatment, so that the first coulomb efficiency of the treated positive electrode plate is 100%;
2) the one-gram charge capacity of the positive electrode material on the treated nickel-containing positive electrode sheet is greater than the first reversible gram capacity before treatment, and the first coulombic efficiency of the treated positive electrode sheet is equal to the reversible gram capacity of the positive electrode material before treatment/the one-gram charge capacity of the positive electrode material after treatment; wherein, the one gram of charge capacity of the treated positive electrode material is the one gram of charge capacity of the positive electrode material before treatment, the gram of charge capacity removed in the charging process of the step (III) and the gram of charge capacity embedded in the discharging process of the step (III).
The method for improving the initial coulomb efficiency of the nickel-containing positive electrode material of the lithium ion battery is applied to design the full battery, and when the full battery is designed, the initial coulomb efficiency of the positive electrode material in the lithium ion full battery is the same as the initial coulomb efficiency of the corresponding negative electrode material, so that the excessive amplitude of the negative electrode material is reduced, and the energy density of the full battery is improved, and the method specifically comprises the following steps:
firstly, placing a positive plate coated with a nickel-containing positive material on a current collector and a counter electrode serving as a lithium carrier in the electrolyte of the lithium ion battery together to form the lithium ion battery;
secondly, connecting a positive terminal of an external power supply with the current collector containing the nickel positive material in the step one, and connecting a negative terminal of the external power supply with the lithium carrier in the step one;
thirdly, the lithium ion battery in the step one is charged and activated by the external power supply in the step two, and lithium ions enter the counter electrode in the step one; discharging the charged lithium ion battery, and returning lithium ions to the nickel-containing positive electrode material on the positive electrode plate in the step (I);
and (IV) taking out the positive plate of the lithium ion battery treated in the steps (I) to (III), and designing and manufacturing the lithium ion full battery relative to the negative plate.
The negative electrode sheet includes, but is not limited to, a lithium foil, a graphitic carbon negative electrode, a silicon negative electrode or a silicon oxide negative electrode, and a negative electrode sheet using a pre-intercalation lithium treatment technique.
Has the advantages that: according to the method, lithium ions in the nickel-containing positive plate are partially removed in advance in a charging and discharging mode, so that the initial coulomb efficiency of the positive material is improved, and the initial reversible gram capacity of the positive material is not reduced. According to the method, the initial coulomb efficiency of the nickel-containing anode material can be adjusted according to needs, so that the excessive amplitude of the cathode material in the design of the full cell is reduced, the initial efficiency matching of the cathode material and the anode material in the design of the full cell is optimal, the volume energy density and the weight energy density of the full cell can be effectively improved, and the method has no degradation influence on the cycle performance of the cell.
Drawings
FIG. 1 is a schematic view of a pretreatment apparatus for a positive electrode sheet.
Detailed Description
The following detailed description of the preferred embodiments will be made in conjunction with the accompanying drawings.
Referring to the drawings in detail, the embodiment provides a method for improving the initial coulomb efficiency of a nickel-containing cathode material of a lithium ion battery, which is characterized in that: lithium ions in the nickel-containing positive plate are partially extracted in advance in a charging and discharging mode, the first charging gram capacity of the nickel-containing positive material is adjusted in the partial lithium ion extracting mode, and the first reversible discharging gram capacity of the positive material is not reduced, so that the first efficiency of the nickel-containing positive material of the lithium ion battery is improved;
the method comprises the following specific steps:
firstly, placing a positive plate coated with a nickel-containing positive material on a current collector and a counter electrode serving as a lithium carrier in the electrolyte of the lithium ion battery together to form the lithium ion battery;
secondly, connecting a positive terminal of an external power supply with the current collector containing the nickel positive material in the step one, and connecting a negative terminal of the external power supply with the lithium carrier in the step one;
thirdly, the lithium ion battery in the step one is charged and activated by the external power supply in the step two, and lithium ions enter the counter electrode in the step one; discharging the charged lithium ion battery, and returning lithium ions to the nickel-containing positive electrode material on the positive electrode plate in the step (I);
the nickel-containing positive electrode material includes, but is not limited to, lithium nickelate, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminate; counter electrodes as lithium carriers include, but are not limited to, lithium foil, graphitic carbon anodes, silicon anodes, or silicon oxide anodes.
The counter electrode functioning as a lithium carrier in the step (one) should have good electrochemical stability in the electrolyte, and preferably, a metallic lithium sheet or foil is used.
An isolating membrane is arranged between the positive plate and the counter electrode, the positive plate and the counter electrode cannot be directly conducted, and the isolating membrane has the properties that lithium ions can pass through and electrons cannot be conducted. The barrier layer can be formed by adding micropores to a PP or PE film, and preferably, the porosity of the PP or PE film is between 20% and 60%.
The external power supply controls the current and voltage applied between the positive plate and the counter electrode, and preferably, a power supply having constant current, constant voltage, and capacity calculation functions is used.
In the step (III), the charging quantity of the charging activation process of the external power supply is between 0 and 100 percent, the discharging quantity of the discharging process is between 0 and 100 percent, and the charging current of the charging process is between 0.01C and 2C, preferably between 0.05C and 0.15C; the discharge current is between 0.01C-2C, preferably between 0.05C-0.15C. The lithium ions can be uniformly extracted and embedded by selecting small current charging and discharging, and the uniformity of the initial coulomb efficiency of the nickel-containing anode material is favorably improved.
In the step (III), in the process of charging the lithium ion battery, lithium ions in the nickel-containing positive electrode material enter the counter electrode in the form of ions or lithium metal, and the amount of lithium ions extracted from the positive electrode material can be adjusted between 0 and 100 percent according to actual requirements. For example, the first efficiency of the nickel cobalt lithium manganate is 85%, the first charge capacity of the manufactured positive plate is 1000mAh, if 10% of the capacity of lithium is removed through the third step, namely 100mAh, and the discharge process in the third step is not performed, the positive plate is used as the positive electrode, the lithium foil is used as the negative electrode to manufacture the lithium ion battery, and the first efficiency of the nickel cobalt lithium manganate positive electrode material measured by the battery is 1000mAh 85%/(1000 mAh-100mAh) — 94.4%, namely the first efficiency of the nickel cobalt lithium manganate material is increased from 85% to 94.4%.
And (3) adjusting the first efficiency of the nickel-containing cathode material by using the step (III) according to requirements. For another example, the first-time efficiency of the nickel-cobalt lithium manganate with 85% is to remove lithium with 15% capacity through the step (three), and the first-time coulombic efficiency of the lithium ion battery manufactured by using the pole piece and the lithium foil negative electrode is 85%/(100% -15%); similarly, lithium with 100% capacity can be removed from the nickel cobalt lithium manganate with the first effect of 85% through the step (three), and then 85% of lithium can be returned to the nickel cobalt lithium manganate positive electrode material through the discharging process in the step (three), so that the nickel cobalt lithium manganate positive electrode material with the first efficiency of 100% can be obtained.
The theoretical first effect calculation method of the positive plate after the treatment of the steps (I) to (III) comprises the following steps:
1) the one-gram charge capacity of the positive electrode material on the treated nickel-containing positive electrode plate is less than the first reversible gram capacity before treatment, so that the first coulomb efficiency of the treated positive electrode plate is 100%;
2) the one-gram charge capacity of the positive electrode material on the treated nickel-containing positive electrode sheet is greater than the first reversible gram capacity before treatment, and the first coulombic efficiency of the treated positive electrode sheet is equal to the reversible gram capacity of the positive electrode material before treatment/the one-gram charge capacity of the positive electrode material after treatment; wherein, the one gram of charge capacity of the treated positive electrode material is the one gram of charge capacity of the positive electrode material before treatment, the gram of charge capacity removed in the charging process of the step (III) and the gram of charge capacity embedded in the discharging process of the step (III).
The method for improving the initial coulomb efficiency of the nickel-containing positive electrode material of the lithium ion battery is adopted to design the application of the full battery, and when the full battery is designed, the initial coulomb efficiency of the positive electrode material in the lithium ion full battery is the same as the initial coulomb efficiency of the corresponding negative electrode material, so that the excessive amplitude of the negative electrode material is reduced, and the energy density of the full battery is improved, and the method specifically comprises the following steps:
firstly, placing a positive plate coated with a nickel-containing positive material on a current collector and a counter electrode serving as a lithium carrier in the electrolyte of the lithium ion battery together to form the lithium ion battery;
secondly, connecting a positive terminal of an external power supply with the current collector containing the nickel positive material in the step one, and connecting a negative terminal of the external power supply with the lithium carrier in the step one;
thirdly, the lithium ion battery in the step one is charged and activated by the external power supply in the step two, and lithium ions enter the counter electrode in the step one; discharging the charged lithium ion battery, and returning lithium ions to the nickel-containing positive electrode material on the positive electrode plate in the step (I);
and (IV) taking out the positive plate of the lithium ion battery treated in the steps (I) to (III), and designing and manufacturing the lithium ion full battery relative to the negative plate.
And (3) adjusting the first coulomb efficiency of the nickel-containing cathode material on the lithium ion battery cathode sheet in the step (IV) to be the same as the first coulomb efficiency of the used cathode sheet. Through the design, the overall volume energy density and the weight energy density of the battery can be optimized under the condition that the first effect of the cathode material and the cathode material is constant.
The negative electrode sheet includes, but is not limited to, a lithium foil, a graphitic carbon negative electrode, a silicon negative electrode or a silicon oxide negative electrode, and a negative electrode sheet using a pre-intercalation lithium treatment technique.
Example 1
As shown in attached figure 1, a mixture ratio of a nickel cobalt lithium manganate NCM523 positive electrode material with a charge capacity of 206mAh/g and a primary efficiency of 85 percent, a binder PVDF2 percent and a conductive agent SP2 percent to a positive electrode material active substance of 96 percent is 16.86mg/cm2The single side of the load is evenly coated on a 12 mu aluminum foil with the effective coating area of 20cm × 15cm, one charge capacity of the pole piece is 1000mAh, the pole piece is placed in electrolyte according to the mode shown in the attached drawing 1, a lithium piece with the thickness of 1mm is taken as a counter electrode, the aluminum foil and the lithium piece are respectively connected to a positive electrode and a negative electrode of an external power supply, the positive electrode is taken out after being charged for 2h by the current of 0.05C, namely 50mAh, and part of the pole piece is taken to manufacture a 2320 button half cell with the lithium piece as the negative electrode to test the reversible capacity of the positive electrode material.
Example 2
As shown in attached figure 1, the nickel cobalt lithium manganate NCM523 positive electrode with the charge capacity of 206mAh/g and the primary efficiency of 85 percent is usedThe mixture ratio of the material, the adhesive PVDF2 percent and the conductive agent SP2 percent to the anode material active substance of 96 percent is 16.86mg/cm2The single side of the load is evenly coated on a 12 mu aluminum foil with the effective coating area of 20cm × 15cm, one charge capacity of the pole piece is 1000mAh, the pole piece is placed in electrolyte according to the mode shown in the attached drawing 1, a lithium piece with the thickness of 1mm is taken as a counter electrode, the aluminum foil and the lithium piece are respectively connected to a positive electrode and a negative electrode of an external power supply, the positive electrode is taken out after being charged for 3h by the current of 0.05C, namely 50mAh, and part of the pole piece is taken to manufacture a 2320 button half cell with the lithium piece as the negative electrode to test the reversible capacity of the positive electrode material.
Example 3
As shown in attached figure 1, a mixture ratio of a nickel cobalt lithium manganate NCM523 positive electrode material with a charge capacity of 206mAh/g and a primary efficiency of 85 percent, a binder PVDF2 percent and a conductive agent SP2 percent to a positive electrode material active substance of 96 percent is 16.86mg/cm2The single side of the load is evenly coated on a 12 mu aluminum foil with the effective coating area of 20cm × 15cm, one charge capacity of the pole piece is 1000mAh, the pole piece is placed in electrolyte according to the mode shown in the attached drawing 1, a lithium piece with the thickness of 1mm is taken as a counter electrode, the aluminum foil and the lithium piece are respectively connected to a positive electrode and a negative electrode of an external power supply, the constant current and the constant voltage of 50mAh are charged to 4.4V by 0.05C, 0.02C is cut off, then the constant current and the constant voltage are discharged to 2.75V by 0.05C, the positive plate is taken out, and part of the pole piece is taken to manufacture a 2320 button half cell with the lithium piece as a negative electrode to test the reversible capacity.
Example 4
Taking a nickel cobalt lithium manganate positive electrode material with the charge capacity of 206mAh/g, the discharge capacity of 175mAh/g and the first coulombic efficiency of 85%, increasing the first coulombic efficiency of the nickel cobalt lithium manganate positive electrode material on a pole piece from 85% to 92%, reducing the first charge capacity to 190mAh/g and reducing the first discharge capacity to 175mAh/g, designing and manufacturing a polymer lithium ion battery with the fixed volume of 4.0mm x 55mm x 82mm by using the pole piece, wherein the diaphragm adopts a 12 mu ceramic diaphragm, the negative electrode adopts natural graphite with the first coulombic efficiency of 92%, the positive electrode active substance proportion is 96%, the binder is 2%, the conductive agent is 2%, the negative electrode current collector adopts 6 mu electrolytic copper foil, the positive electrode current collector adopts 12 mu aluminum foil, the negative electrode active substance proportion is 97%, and the negative electrode-to-positive electrode excess ratio (N/P ratio) is 1.06.
Comparative example 1
Mixing a nickel cobalt lithium manganate NCM523 positive electrode material with the first charge capacity of 206mAh/g and the first efficiency of 85 percent, a binder PVDF2 percent and a conductive agent SP2 percent according to the proportion of 16.86mg/cm of a positive electrode material active substance of 96 percent2The single side of the loading amount of the positive plate is coated on a 12 mu aluminum foil with the effective coating area of 20cm x 15cm, and the reversible capacity of the positive material is tested by taking part of the positive plate to manufacture a 2320 button half cell taking a lithium plate as a negative electrode.
Comparative example 2
A nickel cobalt lithium manganate positive electrode material with the charge capacity of 206mAh/g, the discharge capacity of 175mAh/g and the primary coulombic efficiency of 85% is taken, a polymer lithium ion battery with the fixed volume of 4.0mm x 55mm x 82mm is designed and manufactured, a 12 mu ceramic diaphragm is adopted as the diaphragm, natural graphite with the primary coulombic efficiency of 92% is adopted as the negative electrode, the proportion of positive active substances is 96%, a binder is 2%, a conductive agent is 2%, a 6 mu electrolytic copper foil is adopted as the negative electrode current collector, a 12 mu aluminum foil is adopted as the positive electrode current collector, the proportion of negative active substances is 97%, and the excess ratio (N/P ratio) of the negative electrode to the positive electrode is 1.06.
First coulombic efficiency test: the test conditions for the first coulombic efficiency of examples 1, 2, 3 and comparative example 1 in this embodiment are: and (3) testing by adopting a 2320 button type half cell at 25 ℃ in a mode of stopping the constant-current and constant-voltage charging at 0.1C, 4.4V and 0.02C and stopping the discharging at 0.1C to 2.75V.
And (3) testing the cycle performance: the test conditions for cycle performance of examples 1, 2, 3 and comparative example 1 in this embodiment are: at 25 ℃, a 2320 button type half cell is tested in a mode of stopping constant-current and constant-voltage charging at 0.1C, 4.4V and 0.02C and stopping discharging from 0.1C to 2.75V, one cycle is counted by charging and discharging, the cycle is stopped for 100 times, and the capacity retention rate of the material after the cycle is calculated.
Designing a battery: in the embodiment 4 and the comparative example 2, the advantages and disadvantages of the schemes are compared by adopting the pole piece after the first effect is improved and the pole piece without the first effect under the same battery size and other relevant conditions for capacity design.
Table 1: electrochemical performance test results of button half-cells fabricated in examples 1, 2, 3 and comparative example 1
Table 2: results of performance tests of batteries designed to manufacture the batteries of example 4 and comparative example 2
Comparative example 1 is a currently used lithium nickel cobalt manganese oxide positive electrode, and compared with examples 1, 2 and 3, the measure of the invention can effectively improve the first efficiency of the lithium nickel cobalt manganese oxide positive electrode. In addition, the first reversible gram capacity of the nickel cobalt lithium manganate material in the embodiment is the same as that of the comparative example, the capacity retention rate is also the same after 100 weeks of circulation, and no degradation occurs.
Comparing example 1 with example 2, it can be seen that the measure of the invention can adjust the first coulomb efficiency of the lithium nickel cobalt manganese oxide positive electrode material by controlling the charging ratio according to the requirement.
Comparing example 2 with example 3, it can be seen that the measure of the present invention can achieve the same effect of adjusting the first coulomb efficiency by adjusting the charge ratio and the discharge ratio, and can adjust the charge and discharge parameters as required.
Comparing example 4 with comparative example 2, it can be seen that the first efficiency of the lithium nickel cobalt manganese oxide positive electrode material is adjusted to be the same as that of the negative electrode, the first efficiency of the full battery is also the same as that of the positive electrode and the negative electrode, the capacity of the battery can be improved to 3006mAh from 2873mAh under the same volume, and the gravimetric energy density is improved to 252Wh/Kg from 243 Wh/Kg.
The above detailed description of the method for improving the first coulombic efficiency of the nickel-containing cathode material of the lithium ion battery with reference to the embodiments is illustrative and not restrictive, and several embodiments can be cited according to the limited scope, so that the changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (8)
1. A method for improving the initial coulomb efficiency of a nickel-containing anode material of a lithium ion battery is characterized in that: lithium ions in the nickel-containing positive plate are partially removed in advance in a charging and discharging mode, the first charging gram capacity of the nickel-containing positive material is adjusted in the partial lithium ion removing mode, and the first reversible discharging gram capacity of the nickel-containing positive material is not reduced, so that the first efficiency of the nickel-containing positive material of the lithium ion battery is improved; adjusting the first coulomb efficiency of the nickel-containing anode material to ensure that the first coulomb efficiency of the nickel-containing anode material in the lithium ion battery is the same as that of the corresponding cathode material;
the method comprises the following specific steps:
firstly, placing a positive plate coated with a nickel-containing positive material on a current collector and a counter electrode serving as a lithium carrier in the electrolyte of the lithium ion battery together to form the lithium ion battery;
secondly, connecting a positive terminal of an external power supply with the current collector containing the nickel positive material in the step one, and connecting a negative terminal of the external power supply with the lithium carrier in the step one;
thirdly, the lithium ion battery in the step one is charged and activated by the external power supply in the step two, and lithium ions enter the counter electrode in the step one; discharging the charged lithium ion battery, and returning lithium ions to the nickel-containing positive electrode material on the positive electrode plate in the step (I); the charging and activating process of the external power supply is characterized in that the charging capacity of the nickel-containing cathode material is calculated as 100%, the amount of lithium ions removed from the cathode material is adjusted within a range of more than 0 and less than 100%, the amount of the lithium ions removed from the cathode material is 100% during the charging and activating process, and the amount of the lithium ions returned to the cathode material is adjusted within a range of more than 0 and less than 100%; the charging current in the charging process is between 0.01C and 2C, and the discharging current is between 0.01C and 2C; the first coulomb efficiency calculation method after the positive plate is processed in the steps (I) to (III) comprises the following steps:
1) the one-gram charge capacity of the positive electrode material on the treated nickel-containing positive electrode plate is less than the first reversible gram capacity before treatment, so that the first coulomb efficiency of the treated positive electrode plate is 100%;
2) the one-gram charge capacity of the positive electrode material on the treated nickel-containing positive electrode sheet is greater than the first reversible gram capacity before treatment, and then the first coulombic efficiency of the treated positive electrode sheet = the reversible gram capacity of the positive electrode material before treatment/the one-gram charge capacity of the positive electrode material after treatment; wherein, the one gram charge capacity of the treated positive electrode material = the one gram charge capacity of the positive electrode material before treatment-the gram charge capacity extracted during the charging process of step (three) + the gram charge capacity embedded during the discharging process of step (three).
2. The method for improving the initial coulomb efficiency of the nickel-containing cathode material of the lithium ion battery as claimed in claim 1, wherein: the nickel-containing anode material is lithium nickelate, lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate; the counter electrode as a lithium carrier is a lithium foil, graphitic carbon negative electrode, silicon negative electrode or silicon oxide negative electrode.
3. The method for improving the initial coulomb efficiency of the nickel-containing cathode material of the lithium ion battery as claimed in claim 1, wherein: the counter electrode used as the lithium carrier adopts a metal lithium sheet.
4. The method for improving the initial coulomb efficiency of the nickel-containing cathode material of the lithium ion battery as claimed in claim 1, wherein: an isolating membrane is arranged between the positive plate and the counter electrode, the isolating membrane is a PP or PE film, and the porosity of the PP or PE film is 20% -60%.
5. The method for improving the initial coulomb efficiency of the nickel-containing cathode material of the lithium ion battery as claimed in claim 1, wherein: the external power supply controls the current and the voltage applied between the positive plate and the counter electrode, and has the functions of constant current, constant voltage and capacity calculation.
6. The method for improving the initial coulomb efficiency of the nickel-containing cathode material of the lithium ion battery as claimed in claim 1, wherein: the charging current in the charging process is between 0.05 and 0.15C; the discharge current is between 0.05C and 0.15C.
7. Use of a lithium ion battery designed according to the method of claim 1, characterized in that: when the lithium ion battery is designed, the initial coulomb efficiency of the anode material in the lithium ion battery is the same as the initial coulomb efficiency of the corresponding cathode material, so that the excessive amplitude of the cathode material is reduced, and the energy density of the lithium ion battery is improved, and the method specifically comprises the following steps:
firstly, placing a positive plate coated with a nickel-containing positive material on a current collector and a counter electrode serving as a lithium carrier in the electrolyte of the lithium ion battery together to form the lithium ion battery;
secondly, connecting a positive terminal of an external power supply with the current collector containing the nickel positive material in the step one, and connecting a negative terminal of the external power supply with the lithium carrier in the step one;
thirdly, the lithium ion battery in the step one is charged and activated by the external power supply in the step two, and lithium ions enter the counter electrode in the step one; discharging the charged lithium ion battery, and returning lithium ions to the nickel-containing positive electrode material on the positive electrode plate in the step (I);
and (IV) taking out the positive plate of the lithium ion battery treated in the steps (I) to (III), and designing and manufacturing the lithium ion battery opposite to the negative plate.
8. The method of claim 7, wherein the method comprises the following steps: the negative plate is lithium foil or a negative plate obtained by adopting a pre-lithium-intercalation treatment technology.
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| CN111912736B (en) * | 2020-07-23 | 2023-08-11 | 蜂巢能源科技有限公司 | Method for testing negative electrode degassing capability of lithium ion battery |
| CN112467103A (en) * | 2020-11-23 | 2021-03-09 | 复旦大学 | Preparation method of high-loading self-supporting thick electrode of ternary cathode material |
| CN114497464B (en) * | 2022-01-29 | 2023-07-21 | 合肥国轩高科动力能源有限公司 | Lithium ion battery positive electrode pulse prelithiation method and lithium ion battery |
| CN115995276B (en) * | 2023-03-22 | 2023-05-23 | 四川新能源汽车创新中心有限公司 | Method and device for determining surface density of lithium battery plate and computer terminal |
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