CN109671999B - Lithium ion battery in-situ pre-lithiation method and lithium ion battery - Google Patents
Lithium ion battery in-situ pre-lithiation method and lithium ion battery Download PDFInfo
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Abstract
The invention discloses an in-situ pre-lithiation method for a lithium ion battery and the lithium ion battery. The method comprises the following steps: (1) matching the silicon-based negative electrode material with the positive electrode material to assemble a lithium ion battery, wherein the lithium insertion capacity of the silicon-based negative electrode material is N1, and the lithium removal capacity is N2; the charge capacity of the anode material is P1, the discharge capacity is P2, N2/N1 is more than P2/P1, N1/P1 is more than N2/P2, the value of N2/P2 is 1.02-1.20, and the value of N1/P1 is 0.85-1.05; (2) activating a lithium ion battery by stages, wherein in the first stage: charging to a capacity not higher than N1/P1 × 100% SOC1Discharging to a lower limit voltage not lower than the design voltage range of the battery; and a second stage: charging to a capacity not higher than 100% SOC2Discharging to lower limit voltage not lower than battery design voltage range, activating for 3-30 weeks. The invention does not increase the manufacturing procedure of the lithium ion battery, and is safe and convenient to operate. The lithium ion battery containing the silicon-based negative electrode subjected to in-situ prelithiation by the method has the characteristics of high energy density, long cycle and the like.
Description
Technical Field
The invention relates to an in-situ pre-lithiation method for a lithium ion battery and the lithium ion battery, and belongs to the technical field of lithium ion batteries.
Background
Lithium ion batteries have the advantages of high specific energy, long cycle life, low self-discharge, and the like, and have been widely used in portable electronic products. In recent years, with the progress of materials and the improvement of production technologies, lithium ion batteries have been widely used in the fields of Electric Vehicles (EVs) and hybrid electric vehicles (PHEVs). The endurance mileage of the pure electric vehicle is directly related to the energy density of the single battery, so that the improvement of the energy density of the single battery is a key for improving the endurance mileage of the pure electric vehicle.
The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte and the like, wherein the selection of the positive electrode material and the negative electrode material is a key factor influencing the energy density of the lithium ion battery. The chemical formula of the lithium-rich manganese-based cathode material is xLi2MnO3·(1-x)LiMO2Wherein M is a transition metal. The lithium-rich manganese-based positive electrode material has the capacity of 250mAh/g and low material cost, and becomes a hot spot of the current research. Research finds that the lithium-rich manganese-based material xLi2MnO3·(1-x)LiMO2Li at the time of initial charge at a charge voltage higher than 4.5V2MnO3The components are activated, the lithium layer is extracted together with lithium in the transition metal, and O is accompanied2To form a layered MnO2And a platform of lithium removal and oxygen removal can appear on a charging curve, so that the specific capacity is higher than 250mAh/g, and during discharging, vacancy generated by oxygen removal is occupied by transition metal cations, so that the re-insertion of part of lithium ions removed during charging is hindered, and the first irreversible capacity loss is caused. The first coulombic efficiency of the lithium-rich manganese-based solid solution positive electrode material is generally low. When the cathode material with low first coulombic efficiency is matched with the cathode material with high first effect, in order to ensure that lithium is not separated out in the charging process of the battery, the discharge capacity of the cathode needs to be greatly excessive, the using amount of the cathode is increased, and the increase of the specific energy of the battery is not facilitated.
Li can be formed by lithium insertion of silicon at normal temperature4Si15The theoretical specific capacity of the alloy is up to 3579mAh/g, which is about ten times of that of the graphite cathode. However, the volume of the silicon material can change greatly in the process of lithium intercalation/deintercalation, and the volume expansion rate in the full lithium state is as high as 260%. Such a large volume change causes the SEI film on the silicon surface to be continuously broken-generated, thereby resulting in low coulombic efficiency during the cycle. Mixing nano silicon (Si) or silicon oxide (SiOx) with graphiteThe material composition, the formed Si/C or SiOx/C composite material can effectively relieve the volume expansion of the Si material, and the Si/C and SiOx/C materials are gradually applied in commercialization at present. Due to the inherent volume change of the silicon material, the SEI film of the silicon carbon or silicon oxygen carbon composite material is still unstable in the early stage of the cycle. Therefore, when the full-cell is formed, the cycling coulomb efficiency rises slowly, the Li loss of the anode is serious, and the capacity attenuation at the early stage of the cycling is quick.
In order to solve the problem of low efficiency of the silicon-based negative electrode at the early stage of the cycle, a common method is to pre-lithiate the silicon-based negative electrode. The currently used prelithiation method is mainly rolling lithium metal powder (SLMP) into the negative electrode, or pre-intercalating lithium into the negative electrode by using an electrochemical method. The methods make the manufacturing process of the battery more complicated, have higher requirements on production environment, increase production cost and have more serious potential safety hazard.
Disclosure of Invention
In order to solve the technical problems of low coulombic efficiency and fast capacity attenuation of the silicon-based negative electrode of the lithium ion battery in the early circulation stage, the invention provides the method for in-situ pre-lithiation of the silicon-based negative electrode of the lithium ion battery, which is feasible and can improve the energy density and the circulation stability of the lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of in-situ prelithiation of a lithium ion battery, the method comprising the steps of:
(1) matching the silicon-based negative electrode material with the positive electrode material to assemble a lithium ion battery, wherein the lithium insertion capacity of the silicon-based negative electrode material is N1, and the lithium removal capacity is N2; the charge capacity of the anode material is P1, the discharge capacity is P2, the first coulombic efficiency N2/N1 of the silicon-based anode material in the lithium intercalation and deintercalation voltage range of the silicon-based anode material is larger than the first coulombic efficiency P2/P1 of the anode material in the charge and discharge voltage range of the silicon-based anode material, and the charge and deintercalation capacity of the anode material meets the following requirements: N1/P1 is less than N2/P2, the value of N2/P2 is 1.02-1.20, and the value of N1/P1 is 0.85-1.05;
(2) activating a lithium ion battery by stages, wherein in the first stage: charging to a capacity not higher than N1/P1 × 100% SOC1Discharged to not less than the design voltage range of the batteryA lower limit voltage of (1), wherein 100% SOC1Represents the capacity of first cycle charging to full state in the designed voltage range; and a second stage: charging to a capacity not higher than 100% SOC2Discharging to lower limit voltage not lower than battery design voltage range, activating for 3-30 weeks with 100% SOC2Representing the discharge capacity of the cell within the design voltage range.
Preferably, in the step (1), the lithium intercalation and deintercalation voltage range of the silicon-based negative electrode material is 5 mV-2.0V, and the charge and discharge voltage range of the positive electrode material is 2.0V-5.0V. The value of N2/P2 is preferably 1.05-1.15, and the value of N1/P1 is preferably 0.90-1.00.
For example, assume that the first coulombic efficiency of the positive electrode material is 75% and the first coulombic efficiency of the negative electrode material is 85%. If the value of N1/P1 is set too high, e.g., 1.10, then the value of N2/P2 is 1.25. At the moment, the discharge capacity of the negative electrode is excessive by 25%, and when an SEI film is formed at the early stage of circulation, the excessive silicon-based negative electrode consumes a large amount of positive active lithium, so that the capacity attenuation at the early stage of circulation is fast; in addition, a large excess of the capacity of the negative electrode leads to an increase in the amount of the negative electrode used, an increase in the weight of the battery, and a decrease in the specific energy of the battery. If the value of N1/P1 is set too low, e.g., 0.80, then N2/P2 is 0.91. Even if the activated lithium ion battery is activated, even if 5% of reversible lithium on the positive electrode is consumed by the silicon-based negative electrode to form SEI, the discharge capacity of the negative electrode is still lower than that of the positive electrode, and when the battery is charged and discharged in a set voltage range, lithium dendrites are easily formed on the negative electrode, so that the safety performance of the battery has serious hidden troubles.
Preferably, in the step (2), the charging and discharging current is 0.01C-0.5C, the pressure of 0.01MPa-3.0MPa is applied, and the temperature is kept at 20-60 ℃ in the whole process.
Preferably, the design voltage range in the step (2) is 1.8V to 5.0V.
The second stage comprises four sub-stages: a) charging to a capacity not higher than 90% SOC2Discharging to a lower limit voltage not lower than the design voltage range of the battery, activating for 1-15 weeks, b) charging to a capacity not higher than 95% SOC2Discharging to a lower limit voltage not lower than the design voltage range of the battery, activating for 1-15 weeks, c) chargingDischarging to the upper limit voltage not higher than the design voltage range of the battery, and activating for 1-3 weeks; d) charging to 20-80% SOC2And the activation is finished.
The silicon-based negative electrode material is at least one of a silicon-carbon composite material, a silicon-oxygen-carbon material and a silicon alloy material; in the silicon-carbon composite material or the silicon alloy material, the mass ratio of the active silicon is 3 wt% -30 wt%, and the corresponding specific capacity is 400 mAh/g-1300 mAh/g; the mass ratio of the active SiOx in the silicon-oxygen-carbon material is 5 wt% -50 wt%, wherein x is more than 0.8 and less than 1.2, and the corresponding specific energy is 400 mAh/g-1000 mAh/g.
The positive electrode material is a metal oxide containing lithium, such as one or a mixture of more of Lithium Manganate (LMO), Lithium Cobaltate (LCO), Lithium Manganese Nickel Oxide (LMNO), lithium nickel cobalt aluminate (Li-NCA), lithium nickel cobalt manganese (Li-NCM) and a lithium-rich manganese-based material.
Specifically, the positive electrode material includes the following materials expressed by a formula: liaA1-bBbD2(0.9≤a≤1，0≤b≤0.5)，LiaE1-bBbO2-cDc(0.9≤a≤1，0≤b≤0.5，0≤c≤0.05)，LiE2-bBbO4-cDc(0≤b≤0.5，0≤c≤0.05)，LiaNi1-b-cCobBcDα(0.9≤a≤1，0≤b≤0.5，0≤c≤0.05，0≤α≤2)，LiaNi1-b- cCobBcO2-αFα(0.9≤a≤1，0≤b≤0.5，0≤c≤0.05，0≤α≤2)，LiaNi1-b-cCobBcO2-αF2(0.9≤a≤1，0≤b≤0.5，0≤c≤0.05，0≤α≤2)，LiaNi1-b-cMnbBcO2-αFα(0.9≤a≤1，0≤b≤0.5，0≤c≤0.05，0≤α≤2)，LiaNi1-b-cMnbBcO2-αFα(0.9≤a≤1，0≤b≤0.5，0≤c≤0.05，0≤α≤2)，LiaNibEcGdO2(0.9≤a≤1，0≤b≤0.9，0≤c≤0.5，0.001≤d≤0.1)，LiaNibCocMndGeO2(0.9≤a≤1，0≤b≤0.9，0≤c≤0.5，0≤d≤0.5，0.001≤d≤0.1)，LiaNiGbO2(0.9≤a≤1，0.001≤b≤0.1)，LiaCoGbO2(0.9≤a≤1，0.001≤b≤0.1)，LiaMnGbO2(0.9≤a≤1，0.001≤b≤0.1)，LiaMn2GbO4(0.9≤a≤1，0.001≤b≤0.1)；QO2，QS2，LiQS2，V2O5，LiV2O5，LiIO2，LiNiVO4And Li: (3-f)J2(PO4)3(f is more than or equal to 0 and less than or equal to 2). Wherein, the letters A, B, D, E, F, G, Q, I and J respectively represent one or more elements, in particular: the letter A represents nickel (Ni), cobalt (Co), manganese (Mn) or any combination of three thereof, the letter B represents nickel (Ni), cobalt (Co), manganese (Mn), aluminum (Al), chromium (Cr), iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V) and rare earth metal elements or any combination thereof, the letter D represents oxygen (O), fluorine (F), sulfur (S), phosphorus (P) or any combination thereof, the letter E represents cobalt (Co), manganese (Mn) or any combination thereof, the letter F represents fluorine (F), sulfur (S), phosphorus (P) or any combination thereof, the letter G represents aluminum (Al), chromium (Cr), manganese (Mn), iron (Fe), magnesium (Mg), lanthanum (La), cerium (Ce), strontium (Sr), vanadium (V) or any combination thereof, the letter Q represents titanium (Ti), molybdenum (Mo) or any combination thereof, the letter I represents chromium (Cr), vanadium (V), iron (Fe), scandium (Sc), yttrium (Y), or any combination thereof, and the letter (J) represents vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), or any combination thereof.
The positive electrode material is a lithium-rich manganese-based positive electrode material or a positive electrode material containing a lithium-rich manganese base, and the general formula of the lithium-rich manganese-based positive electrode material is xLi2MnO3·(1-x)LiMO2Wherein x is more than 0 and less than 1, M is transition metal, and can be one or more of nickel, cobalt, manganese, iron, boron, aluminum and vanadium.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the positive electrode is the electrode of the invention, and the negative electrode is a silicon-based negative electrode in-situ pre-lithiated by adopting the method.
In the lithium ion battery, the diaphragm is an electronic insulation material with low transmission impedance to lithium ions in the electrolyte and good absorption and wettability to the electrolyte. The diaphragm material can be at least one of glass fiber, polyester fiber, polytetrafluoroethylene, polyethylene, polypropylene, polyimide and aramid fiber material. The pore size of the membrane is generally distributed between 0.1 μm and 10 μm, and the thickness is generally distributed between 5 μm and 300. mu.m.
In the lithium ion battery of the present invention, the electrolyte includes a nonaqueous electrolyte and a lithium salt, wherein the nonaqueous electrolyte may be a nonaqueous electrolyte solution, an organic solid electrolyte, or an inorganic solid electrolyte.
The invention has the advantages that:
compared with other pre-lithiation methods, the method does not change the preparation process of the lithium ion battery and does not improve the environmental requirement in the preparation process of the lithium ion battery. The process is simple, safe and reliable. According to the lithium ion battery prepared by the method, due to the fact that in-situ pre-lithiation of the silicon-based negative electrode is achieved, the cycle performance is improved, meanwhile, the using amount of negative electrode active materials is reduced, and the energy density of the lithium ion battery is improved.
Drawings
Fig. 1 shows the cycle performance curves of example 1 for a cell designed to have an N2/P2 of 1.05 and an N1/P1 of 0.90 and comparative example 1 for a cell designed to have an N2/P2 of 1.05 and an N1/P1 of 0.90 at 0.3C/1.0C, 2.0 to 4.6V.
Fig. 2 is a discharge curve of the battery for the last week before the end of activation.
Fig. 3 shows the cycling performance curves at 0.3C/1.0C, 2.0-4.6V for the cell of example 1 with a design N2/P2 of 1.05 and N1/P1 of 0.90 and for the cell of comparative example 2 with a design N2/P2 of 1.25 and N1/P1 of 1.075.
Detailed Description
For a further understanding of the present invention, embodiments of the present invention are described below in conjunction with the examples, but it is to be understood that these descriptions are intended only to further illustrate features and advantages of the present invention, and are not intended to limit the claims of the present invention.
Example 1
Taking a silicon-carbon composite material with 15 percent of active silicon content as a negative electrode material and a lithium-rich manganese-based material 0.4Li2MnO3·0.6Li(Ni0.33Co0.33Mn0.33)O2As a cathode material, N1/P1 was designed to be 0.90(N2/P2 was 1.05), and a soft-packed lithium ion battery having a roll-to-roll structure was prepared.
Wherein the silicon-carbon composite material with 15 percent of active silicon content has the first coulombic efficiency of 85 percent and the reversible specific capacity (N2) of 850mAh/g in the voltage range of 5 mV-1.5V; lithium-rich manganese-based material 0.4Li2MnO3·0.6Li(Ni0.33Co0.33Mn0.33)O2In the voltage range of 2.0-4.8V, the first coulombic efficiency is 73%, and the reversible specific capacity (P2) is 230 mAh/g.
The designed charge capacity of the prepared lithium ion battery is 100 percent SOC (state of charge) from first cycle charging to full state in the voltage range of 2.0-4.7V and under the multiplying power of 0.1C1At 3.7Ah, the discharge capacity was designed to be 100% SOC2It was 2.7 Ah.
The prepared cell was activated in stages:
the first stage is as follows: the battery was charged to 3.145Ah (85% SOC) at 0.05C under 0.3MPa1) (ii) a Maintaining the pressure, discharging to 2.0V at a current of 0.05C, and controlling the temperature of the whole process at 25 ℃;
and a second stage: a) the battery was charged to 2.4Ah (89% SOC) at 0.1C under 0.3MPa2) Maintaining the pressure, discharging to 2.0V at 0.1C, and activating for 5 weeks; b) the battery was charged to 2.55Ah (94% SOC) at 0.1C under 0.3MPa2) Maintaining the pressure, discharging to 2.0V at 0.1C, and activating for 5 weeks; c) applying 0.3Mpa to the battery, charging to 4.7V at 0.1C, maintaining pressure, discharging to 2.0V at 0.1C, and activating for 1 week; d) the battery was charged to 1.35Ah (50% SOC) at 0.1C under 0.3MPa2) End afterAnd (4) activating. The temperature of the whole process is controlled at 25 ℃.
The battery after completion of activation was degassed and heat-sealed, and then subjected to cycle performance test under a 0.3C/1.0C, 2.0-4.6V regime, and the results are shown in FIG. 1. The discharge curves for the last week of activation are normalized as shown in figure 2.
Comparative example 1
Taking a silicon-carbon composite material with 15 percent of active silicon content as a negative electrode material and a lithium-rich manganese-based material 0.4Li2MnO3·0.6Li(Ni0.33Co0.33Mn0.33)O2As a cathode material, N1/P1 was designed to be 0.90(N2/P2 was 1.05), and a soft-packed lithium ion battery having a roll-to-roll structure was prepared.
Wherein the silicon-carbon composite material with 15 percent of active silicon content has the first coulombic efficiency of 85 percent and the reversible specific capacity (N2) of 850mAh/g in the voltage range of 5 mV-1.5V; lithium-rich manganese-based material 0.4Li2MnO3·0.6Li(Ni0.33Co0.33Mn0.33)O2In the voltage range of 2.0-4.8V, the first coulombic efficiency is 73%, and the reversible specific capacity (P2) is 230 mAh/g.
The prepared lithium ion battery is charged to 100% of capacity SOC in a full state in a first cycle within a voltage range of 2.0-4.7V13.7Ah, discharge capacity 100% SOC2It was 2.7 Ah.
Activating the prepared battery:
applying 0.3Mpa to the battery, and charging to 4.7V at a current of 0.05C; the pressure was maintained and the discharge was made to 2.0V at a current of 0.05C. Applying 0.3Mpa to the battery, and charging to 4.7V at a current of 0.1C; the pressure was maintained, the discharge was carried out at a current of 0.1C to 2.0V, and the activation was carried out for 11 weeks. The temperature of the whole process is controlled at 25 ℃.
The battery after completion of activation was degassed and heat-sealed, and then subjected to cycle performance test under a 0.3C/1.0C, 2.0-4.6V regime, and the results are shown in FIG. 1. The discharge curves for the last week of activation are normalized as shown in figure 2.
As can be seen from fig. 1, the cycle stability of example 1 is superior to that of comparative example 1. As can be seen from fig. 2, lithium deposition still occurs in the negative electrode in comparative example 1 in the last week after the formation is finished, while no lithium deposition occurs in example 1 at the end of the formation. Comparative example 1 lithium precipitation occurred during the activation stage and the cycle performance was inferior to example 1.
Comparative example 2
Taking a silicon-carbon composite material with 15 percent of active silicon content as a negative electrode material and a lithium-rich manganese-based material 0.4Li2MnO3·0.6Li(Ni0.33Co0.33Mn0.33)O2As a cathode material, N1/P1 ═ 1.075(N2/P2 is 1.25) was designed, and a soft-packed lithium ion battery of a roll-to-roll structure was prepared.
Wherein the silicon-carbon composite material with 15 percent of active silicon content has the first coulombic efficiency of 85 percent and the reversible specific capacity (N2) of 850mAh/g in the voltage range of 5 mV-1.5V; lithium-rich manganese-based material 0.4Li2MnO3·0.6Li(Ni0.33Co0.33Mn0.33)O2In the voltage range of 2.0-4.8V, the first coulombic efficiency is 73%, and the reversible specific capacity (P2) is 230 mAh/g.
The prepared lithium ion battery is charged to 100% of capacity SOC in a full state in a first cycle within a voltage range of 2.0-4.7V13.7Ah, discharge capacity 100% SOC2It was 2.7 Ah.
The prepared cell was activated in stages:
the first stage is as follows: the battery was charged to 3.145Ah (85% SOC) at 0.05C under 0.3MPa1) (ii) a Maintaining the pressure, discharging to 2.0V at a current of 0.05C, and controlling the temperature of the whole process at 25 ℃;
and a second stage: a) the battery was charged to 2.4Ah (89% SOC) at 0.1C under 0.3MPa2) Maintaining the pressure, discharging to 2.0V at 0.1C, and activating for 5 weeks; b) the battery was charged to 2.55Ah (94% SOC) at 0.1C under 0.3MPa2) Maintaining the pressure, discharging to 2.0V at 0.1C, and activating for 5 weeks; c) applying 0.3Mpa to the battery, charging to 4.7V at 0.1C, maintaining pressure, discharging to 2.0V at 0.1C, and activating for 1 week; d) the battery was charged to 1.35Ah (50% SOC) at 0.1C under 0.3MPa2) And then the activation is finished. The temperature of the whole process is controlled at 25 ℃.
Claims (8)
1. An in-situ prelithiation method for a lithium ion battery, the method comprising the steps of:
(1) matching the silicon-based negative electrode material with the positive electrode material to assemble a lithium ion battery, wherein the lithium insertion capacity of the silicon-based negative electrode material is N1, and the lithium removal capacity is N2; the charge capacity of the anode material is P1, the discharge capacity is P2, the first coulombic efficiency N2/N1 of the silicon-based anode material in the lithium intercalation and deintercalation voltage range of the silicon-based anode material is larger than the first coulombic efficiency P2/P1 of the anode material in the charge and discharge voltage range of the silicon-based anode material, and the charge and deintercalation capacity of the anode material meets the following requirements: N1/P1< N2/P2, the value of N2/P2 is 1.02-1.20, and the value of N1/P1 is 0.85-1.05;
(2) activating a lithium ion battery by stages, wherein in the first stage: charging to a capacity not higher than N1/P1 × 100% SOC1Discharging to a lower limit voltage not lower than a design voltage range of the battery, wherein the SOC is 100%1Represents the capacity of first cycle charging to full state in the designed voltage range; and a second stage: charging to a capacity not higher than 100% SOC2Discharging to a lower limit voltage not lower than a design voltage range of the battery, wherein the SOC is 100%2Represents the discharge capacity of the battery in the designed voltage range; the second stage comprises four sub-stages: a) charging to a capacity not higher than 90% SOC2Discharging to a lower limit voltage not lower than the design voltage range of the battery, activating for 5-15 weeks, b) charging to a capacity not higher than 95% SOC2Discharging to a lower limit voltage not lower than a design voltage range of the battery, and activating for 5-15 weeks, c) charging to an upper limit voltage not higher than the design voltage range of the battery, discharging to a lower limit voltage not lower than the design voltage range of the battery, and activating for 1-3 weeks; d) charging to 20-80% SOC2And the activation is finished.
2. The in-situ prelithiation method of li-ion battery as claimed in claim 1, wherein in step (1), the voltage range of lithium intercalation and deintercalation of silicon-based negative electrode material is 5mV to 2.0V, and the voltage range of positive electrode material charging and discharging is 2.0V to 5.0V; the value of N2/P2 is 1.05-1.15, and the value of N1/P1 is 0.90-1.00.
3. The method for in-situ prelithiation of li-ion battery according to claim 1, wherein in step (2), the charging and discharging current is 0.01-0.5C, a pressure of 0.01-3.0 MPa is applied, and the temperature is maintained at 20-60 ℃ throughout the process.
4. The method for in-situ prelithiation of a lithium ion battery according to claim 1, wherein the design voltage in step (2) is in the range of 1.8V to 5.0V.
5. The method of in-situ prelithiation of a lithium ion battery according to claim 1, wherein the silicon-based negative electrode material is at least one of a silicon-carbon composite material, a silicon-oxygen-carbon material, and a silicon alloy material; in the silicon-carbon composite material or the silicon alloy material, the mass ratio of the active silicon is 3 wt% -30 wt%, and the corresponding specific capacity is 400 mAh/g-1300 mAh/g; the mass ratio of the active SiOx in the silicon-oxygen-carbon material is 5 wt% -50 wt%, wherein x is more than 0.8 and less than 1.2, and the corresponding specific energy is 400 mAh/g-1000 mAh/g.
6. The method of in-situ prelithiation of a li-ion battery according to claim 1, wherein the positive electrode material is one or a mixture of lithium manganate, lithium cobaltate, li-mn-ni oxide, li-ni-co-al aluminate, li-ni-co-mn, li-rich-mn based material.
7. The method of in-situ prelithiation of a lithium ion battery according to claim 1, wherein the positive electrode material is a lithium-rich manganese-based positive electrode material or a positive electrode material comprising a lithium-rich manganese-based positive electrode material having a general formula of xLi2MnO3·(1-x)LiMO2Wherein 0 is<x<1, M is one or more of nickel, cobalt, manganese, iron, boron, aluminum and vanadium.
8. A lithium ion battery comprising a silicon-based negative electrode prelithiated in situ using the method of any one of claims 1 to 7.
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| CN112242551B (en) * | 2019-07-16 | 2021-12-07 | 宁德时代新能源科技股份有限公司 | Secondary battery |
| KR20210011245A (en) * | 2019-07-22 | 2021-02-01 | 주식회사 엘지화학 | Method for manufacturing secondary battery |
| CN110518189B (en) * | 2019-10-23 | 2020-02-14 | 湖南省正源储能材料与器件研究所 | Device and method for simultaneously realizing pre-deoxidation of anode material and pre-lithiation of cathode material |
| CN111856293B (en) * | 2020-06-03 | 2022-12-06 | 天津力神电池股份有限公司 | Method for testing capacity of silicon negative electrode material of lithium ion battery |
| CN111769332B (en) * | 2020-06-29 | 2021-12-14 | 合肥国轩高科动力能源有限公司 | Formation method of pre-lithium battery and pre-lithiation lithium ion battery |
| CN112034020A (en) * | 2020-08-19 | 2020-12-04 | 国联汽车动力电池研究院有限责任公司 | Method and device for measuring lithium pre-intercalation amount of negative electrode of lithium ion battery |
| US11831001B2 (en) | 2021-05-13 | 2023-11-28 | Saft America | Pre-lithiation method and pre-lithiated lithium-ion secondary battery |
| CN113471561B (en) * | 2021-07-01 | 2023-06-27 | 四川长虹电源有限责任公司 | Method for determining activation process of lithium ion battery |
| CN113540591B (en) * | 2021-09-17 | 2021-12-17 | 中航锂电科技有限公司 | Lithium ion battery lithium supplementing method |
| WO2024108371A1 (en) * | 2022-11-22 | 2024-05-30 | 宁德时代新能源科技股份有限公司 | Electrode assembly, secondary battery and electric apparatus |
| WO2024108372A1 (en) * | 2022-11-22 | 2024-05-30 | 宁德时代新能源科技股份有限公司 | Electrode assembly, secondary battery, and electric device |
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