CN111653842B - Low-self-discharge-rate lithium ion battery formation method and ternary soft-package lithium ion battery - Google Patents
Low-self-discharge-rate lithium ion battery formation method and ternary soft-package lithium ion battery Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a low-self-discharge-rate lithium ion battery formation method and a ternary soft package lithium ion battery. The formation method comprises the following steps: after the battery cell is injected with liquid, standing for 40-48 h at the temperature of 22-28 ℃; sequentially charging the battery cell by using currents of 0.01-0.03C, 0.04-0.06C and 0.08-0.1C, and finally charging to 40% -60% SOC for the last time; primary degassing; charging the battery cell by using 0.2-0.5C current until the SOC reaches 100%; standing at the temperature of 33-38 ℃ for 40-48 h, and then cooling at normal temperature; and (5) secondary degassing. The formation method can effectively relieve the self-discharge problem of the lithium ion battery; the ternary soft package lithium ion battery adopts a novel electrolyte additive, and self-discharge can be further reduced by replacing carbon atoms between two sulfur atoms in MMDS with nitrogen atoms.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a low-self-discharge-rate lithium ion battery formation method and a ternary soft package lithium ion battery.
Background
The lithium ion battery as an efficient energy storage and conversion device has the advantages of high energy density, good cycle performance, low self-discharge rate, no memory effect, environmental friendliness and the like, and is widely applied to the fields of consumer electronics, electric automobiles, power station energy storage power systems, uninterruptible power supplies, military equipment and the like.
Self-discharge refers to a phenomenon that capacity is naturally lost in the storage process of a battery without an external circuit. The self-discharge can affect the capacity, internal resistance and the like of the battery, and the consistency of the self-discharge rate of each single battery can affect the performance of the battery module; in addition, severe self-discharge can lead to thermal runaway of the battery, causing safety issues for parking the electric vehicle. Self-discharge of lithium ion batteries includes reversible self-discharge and irreversible self-discharge. The former can be compensated by recharging, mainly due to physical reasons; the latter cannot be compensated by recharging, mainly because of the complex side reactions occurring inside the battery, resulting in a reduction of active lithium.
After the lithium ion battery is manufactured, the lithium ion battery needs to be activated by first charging and discharging, and then the lithium ion battery is formed. The formation process mainly comprises the steps of converting lithium ions in the active material of the battery into ions with normal electrochemical action; meanwhile, the electrolyte solvent, the electrolyte anion and the lithium salt undergo side reaction to form a Solid Electrolyte Interface (SEI) film on the surface of the negative electrode, and the following two typical side reaction equations are shown: 2CH3CH2OCO2CH3+2e-+2Li+→2CH3CH2OCO2Li↓+C2H6↑， PF6 -+e-+2Li+→LiF↓+LiPF6(ii) a In addition, the electrolyte is also oxidized and decomposed by the positive electrode material, and a layer of SEI film rich in lithium is formed on the surface of the positive electrode. The SEI film of the negative electrode can separate the negative electrode from the electrolyte, so that the transfer of electrons from the negative electrode to the electrolyte and the transfer of solvent molecules and electrolyte anions to the negative electrode are reduced, namely the electrons are separated from the electrolyte solvent, the further occurrence of side reactions is prevented, and the loss of lithium ions is reduced; the SEI film of the anode can separate the anode material from the electrolyte, prevent the anode material and the electrolyte from continuing to react and reduce the loss of lithium ions. Thus, the formation process is self-sustaining to the lithium ion batteryThe discharge rate has a significant effect.
Chinese patent publication No. CN103855431A discloses a formation method for improving cycle performance of a lithium ion battery, which includes the following steps: (1) charging the lithium ion battery at a current of 0.01-0.1C, and keeping the SOC between 5% and 15% after charging; then charging the battery with a current of 0.1-0.5C, and keeping the SOC between 40-60% after charging; (2) carrying out first pre-air-extraction sealing treatment on the lithium ion battery; (3) charging the lithium ion battery with a current of 0.2-1.0C, wherein the SOC reaches 100% after charging; (4) aging the lithium ion battery, and then performing secondary pre-pumping and sealing treatment; the temperature of the aging treatment is 40-60 ℃, and the time is 12-36 h; (5) carrying out floating charge on the lithium ion battery by using a current of 0.01-0.1C, and carrying out aging treatment after floating charge; (6) and then the lithium ion battery is subjected to air pumping and sealing treatment. The self-discharge rate of the battery cell obtained by the formation method is high, and the reason is presumed as follows: the aging treatment time is short, the SEI film is unstable after reforming, and the process of consuming active lithium due to continuous repair can cause the increase of the self-discharge rate.
Disclosure of Invention
In order to solve the technical problems, the invention provides a lithium ion battery formation method with low self-discharge rate and a ternary soft package lithium ion battery. The formation method can effectively relieve the self-discharge problem of the lithium ion battery; the ternary soft package lithium ion battery can further reduce the self-discharge of the battery by adding a novel electrolyte additive.
The specific technical scheme of the invention is as follows:
a low self-discharge rate lithium ion battery formation method comprises the following steps:
(1) normal temperature infiltration: after the battery cell is injected with liquid, standing for 40-48 h at the temperature of 22-28 ℃;
(2) the method comprises the following steps of (1) one-time formation: sequentially using currents of 0.01-0.03C, 0.04-0.06C and 0.08-0.1C to charge the battery cell, and finally charging to 40% -60% SOC for the first time;
(3) primary degassing: firstly rolling the cell main body, discharging internal gas, and then vacuumizing;
(4) carrying out secondary formation: charging the battery cell by using a current of 0.2-0.5C until the battery cell is charged to 100% SOC;
(5) and (3) high-temperature aging: standing at the temperature of 33-38 ℃ for 40-48 h, and then cooling at normal temperature;
(6) secondary degassing: and rolling the cell main body, discharging internal gas, and vacuumizing.
After the battery is subjected to the pre-charging process, the battery needs to be left for aging at a high temperature so that the SEI film is reformed to form the SEI film with more stable properties and composition. In the existing formation method, the high-temperature shelf aging time after pre-charging is usually 12-36 h, the high-temperature aging time is short, although the production period can be shortened, the SEI film is unstable after reforming, the SEI film can be continuously damaged in the storage process, the electrolyte solvent, electrolyte anions and lithium ions continue to generate side reaction at the negative electrode, the electrolyte, the positive electrode material and the lithium ions continue to generate side reaction at the positive electrode, a new precipitate repairing SEI film is formed, and active lithium in the battery is continuously consumed by the cycle, so that irreversible self-discharge loss is caused. In the step (5), the high-temperature aging time is adjusted to 40-48 h, and the SEI film can be more stable by prolonging the high-temperature aging time, so that the consumption of active lithium caused by continuous repair of the SEI film is avoided, and the self-discharge rate can be reduced.
In addition, during the formation process of the negative SEI film, a dense film structure is formed on the inner layer close to the electrode surface, and a loose film structure is formed on the outer layer close to the electrolyte side. The formation method adopts twice formation, and different currents are selected for charging respectively aiming at two stages of the negative electrode SEI film formation process, so that the formed negative electrode SEI film has better film formation quality. And the first formation is divided into three stages, the current of each stage is gradually increased, and compared with the prior art, the current of each stage is smaller, so that the inner layer of the SEI film of the negative electrode is more compact, the negative electrode and the electrolyte are better separated, the transfer of electrons from the negative electrode to the electrolyte and the transfer of solvent molecules and electrolyte anions to the negative electrode are reduced, further side reactions in the storage process are prevented, the loss of active lithium is reduced, and self-discharge is reduced. The second formation fully charges the battery, can ensure complete film forming reaction of the positive and negative SEI films, and the formed SEI film is more stable, so that active lithium is prevented from being consumed due to continuous repair of the SEI film in the storage process, and self-discharge can be reduced.
Preferably, in the step (3), the rolling pressure is 0.2-0.3 MPa during rolling; and when vacuumizing, the vacuum degree is 25-47 Torr, and the time for keeping the vacuum is 5-8 s.
Preferably, in the step (6), the rolling pressure is 0.2-0.3 MPa during rolling; and when the vacuum is pumped, the vacuum degree is 5-15 Torr, and the time for keeping the vacuum is 10-15 s.
The ternary soft-package power lithium ion battery prepared by the formation method comprises a positive electrode, a negative electrode, a diaphragm and electrolyte.
Preferably, the electrolyte includes a lithium salt and an organic solvent; the lithium salt is lithium hexafluorophosphate; the organic solvent is at least one of ethylene carbonate and dimethyl carbonate.
Preferably, the electrolyte comprises an electrolyte additive, and the electrolyte additive has a structural formula:
wherein X is any one of the following cases:
a straight chain or branched chain alkyl group with 1-5 carbon atoms;
a linear or branched alkoxy group having 1 to 5 carbon atoms;
a straight or branched alkyl group in which some or all of the hydrogens are substituted with halogen atoms;
phenyl or substituted phenyl;
a carbonate group or a carbonate group substituted with a halogen atom;
a halogen atom;
a hydrogen atom.
The continuous damage and repair of the SEI film of the anode of the lithium ion battery are also an important reason for the loss of active lithium, and particularly when the anode material is a high-nickel ternary material, the SEI film of the anode is easy to crack, so that the anode is contacted with the electrolyte again, and the interface side reaction is continuously carried out, so that the irreversible self-discharge is caused. High temperature also causes deterioration of the SEI film to be aggravated, resulting in repair and growth of the SEI film, which results in loss of active lithium. In addition, in a high-temperature environment, an oxidation-reduction reaction occurs between the anode of the lithium ion battery and the electrolyte, so that the valence state of the transition metal in the anode material is changed, some transition metal with new valence state can be dissolved into the electrolyte at high temperature, the loss of the anode active material is caused, and the reduction of the battery capacity, namely self-discharge, can also be caused. This problem can be improved by adding a positive electrode film-forming additive to the electrolyte.
The electrolyte additive adopted in the invention is obtained by improving the existing positive electrode film-forming additive Methyl Methylene Disulfonate (MMDS), and the carbon atom between two sulfur atoms in the MMDS molecule is replaced by a nitrogen atom, so that the electronegativity of the nitrogen atom is stronger than that of the carbon atom, and the electron deviation degree to the nitrogen atom is larger after the nitrogen atom is bonded with the sulfur atom, thus the electrophilicity of the sulfur atom can be increased, the structure is easier to be reduced under low voltage during formation, and is prior to the oxidative decomposition of solvent molecules to form an SEI film on the surface of a positive electrode, so that the film-forming reaction of the SEI film is more complete under the same formation time; also, it has been found through experiments that the electrolyte additive of the present invention can better improve the self-discharge problem of the lithium ion battery, probably because the SEI film formed by the electrolyte additive of the present invention is more dense and stable than the SEI film formed by solvent molecules and the SEI film formed by MMDS.
Preferably, the dosage of the electrolyte additive is 0.01-10% of the total mass of the electrolyte.
Preferably, the concentration of the lithium salt is 0.5-1.3 mol/L.
Preferably, the organic solvent accounts for 80-90% of the total mass of the electrolyte.
Preferably, the positive electrode comprises a positive active material, and the positive active material is a nickel-cobalt-manganese composite material; and/or the negative electrode comprises a negative active material, the negative active material being graphite; and/or the diaphragm is a ceramic-coated polypropylene composite diaphragm.
Compared with the prior art, the invention has the following advantages:
(1) the formation method of the invention charges the battery to full charge during the second formation, so that the film forming reaction of the SEI films of the anode and the cathode is more complete, the film forming quality is better, the anode and the cathode can be better separated from the electrolyte, the film forming reaction is avoided from further happening, and the self-discharge rate of the battery is reduced;
(2) according to the formation method, the first formation is divided into three stages, and the high-temperature aging time is prolonged, so that the generated positive and negative SEI is more stable, the loss of active lithium caused by continuous damage and repair of an SEI film is avoided, and the self-discharge rate of the battery is reduced;
(3) according to the ternary soft package lithium ion battery, the new electrolyte additive is added into the electrolyte, so that the formation and the stability of the positive electrode SEI film are facilitated, the positive electrode and the electrolyte can be better separated, the loss of active lithium caused by continuous damage and repair of the positive electrode SEI film can be avoided, and the self-discharge rate of the battery is reduced.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
The ternary soft package lithium ion battery is prepared through the following steps, and self-discharge evaluation is carried out after formation:
(1) preparing a ternary soft package lithium ion battery:
(1.1) preparing an electrolyte: taking at least one of ethylene carbonate and dimethyl carbonate as an organic solvent, and adding lithium hexafluorophosphate to ensure that the concentration of the lithium hexafluorophosphate is 0.5-1.3 mol/L;
preferably, adding an electrolyte additive into the lithium hexafluorophosphate solution, wherein the using amount of the electrolyte additive is 0.01-10% of the total mass of the electrolyte, uniformly mixing until the solid is completely dissolved, and the structural formula of the electrolyte additive is as follows:
wherein X is any one of the following cases:
a straight chain or branched chain alkyl group with 1-5 carbon atoms;
a linear or branched alkoxy group having 1 to 5 carbon atoms;
a straight or branched alkyl group in which some or all of the hydrogens are substituted with halogen atoms;
phenyl or substituted phenyl;
a carbonate group or a carbonate group substituted with a halogen atom;
a halogen atom;
a hydrogen atom;
(1.2) preparing a positive pole piece: preparing a positive pole piece by taking a nickel-cobalt-manganese synthetic material as a positive active material;
(1.3) preparing a negative pole piece: preparing a negative pole piece by taking graphite as a negative active material;
(1.4) preparing a separator: preparing a diaphragm by coating a ceramic layer on a polypropylene layer;
(1.5) assembling a battery core: assembling a positive pole piece, a diaphragm, a negative pole piece, a tab and an aluminum plastic film into a dry battery cell;
(2) formation:
(2.1) normal temperature infiltration: after the battery cell is injected with liquid, standing for 40-48 h at the temperature of 22-28 ℃;
(2.2) one-time formation: sequentially using currents of 0.01-0.03C, 0.04-0.06C and 0.08-0.1C to charge the battery cell, and finally charging to 40% -60% SOC for the first time;
(2.3) primary degassing: firstly rolling the cell main body, and discharging internal gas into a gas bag, wherein the rolling pressure is 0.2-0.3 MPa; vacuumizing, wherein the vacuum degree is 25-47 Torr, and the vacuum maintaining time is 5-8 s;
(2.4) secondary formation: charging the battery cell by using 0.2-0.5C current until the SOC reaches 100%;
(2.5) high-temperature aging: standing at the temperature of 33-38 ℃ for 40-48 h, and then cooling at normal temperature;
(2.6) secondary degassing: firstly rolling the cell main body, and discharging internal gas into a gas bag, wherein the rolling pressure is 0.2-0.3 MPa; vacuumizing, wherein the vacuum degree is 5-15 Torr, and the vacuum maintaining time is 10-15 s;
(3) capacity grading: charging to 4.2V by using a 0.3C constant current and constant voltage, then discharging to 2.7V by using a 0.3C constant current, and then charging to 4.2V by using a 0.3C constant current and constant voltage, and cutting off the current to 0.05C;
(4) self-discharge evaluation: and (3) after the mixture is placed for 22-26 hours at the temperature of 20-26 ℃, testing the open-circuit voltage, and recording the open-circuit voltage as OCV 1: after the mixture is placed for 44-52 hours at the temperature of 20-26 ℃, testing the open-circuit voltage, and marking as OCV 2; open circuit voltage decay OCV1-OCV 2.
Example 1
The ternary soft package lithium ion battery is prepared through the following steps, and self-discharge evaluation is carried out after formation:
(1) preparing a ternary soft package lithium ion battery:
(1.1) preparing an electrolyte: adding lithium hexafluorophosphate into ethylene carbonate to make the concentration of lithium hexafluorophosphate be 1 mol/L;
(1.2) preparing a positive pole piece: LiNi of nickel cobalt lithium manganate is mixed according to the ratio of 93:3:40.8Co0.1Mn0.1O2Dispersing PVDF and a conductive agent in N-methyl pyrrolidone to obtain positive electrode slurry; uniformly coating the positive electrode slurry on an aluminum foil, drying, rolling, slitting and punching to obtain a positive electrode plate;
(1.3) preparing a negative pole piece: dispersing artificial graphite, carboxymethyl cellulose and a conductive agent in water according to a ratio of 95:2:3, and uniformly stirring to obtain negative electrode slurry; uniformly coating the negative electrode slurry on a copper foil, drying, rolling, slitting and punching to obtain a negative electrode pole piece;
(1.4) preparing a separator: coating the ceramic on the two sides of the polypropylene layer, and drying to obtain the diaphragm;
(1.5) assembling a battery core: winding a sandwich structure consisting of the positive pole piece, the diaphragm and the negative pole piece, flattening the wound cylinder, welding a tab, packaging by using an aluminum-plastic film to obtain a dry cell, and drying in vacuum at 85 ℃;
(2) formation:
(2.1) normal temperature infiltration: after the battery core is injected with liquid, standing for 45 hours at the temperature of 25 ℃;
(2.2) one-time formation: sequentially using currents of 0.01C, 0.05C and 0.1C to charge the battery cell, and finally charging to 50% SOC (namely 3.8V) for the first time;
(2.3) primary degassing: firstly rolling the cell main body, and discharging internal gas into a gas bag, wherein the rolling pressure is 0.2 MPa; vacuumizing again, wherein the vacuum degree is 47Torr, and the vacuum maintaining time is 6 s;
(2.4) secondary formation: charging the cell to 100% SOC (i.e. 4.2V) using 0.3C current;
(2.5) high-temperature aging: standing at 35 deg.C for 45h, and cooling at room temperature;
(2.6) secondary degassing: firstly rolling the cell main body, and discharging internal gas into a gas bag, wherein the rolling pressure is 0.2 MPa; vacuumizing, wherein the vacuum degree is 10Torr, and the vacuum maintaining time is 10 s;
(3) capacity grading: charging to 4.2V by using a 0.3C constant current and constant voltage, then discharging to 2.7V by using a 0.3C constant current, and then charging to 4.2V by using a 0.3C constant current and constant voltage, and cutting off the current to 0.05C;
(4) self-discharge evaluation: after 22h at 25 ℃, the open circuit voltage was tested and reported as OCV 1: after the mixture is placed for 50 hours at the temperature of 25 ℃, the open-circuit voltage is tested and is marked as OCV 2; open circuit voltage decay OCV1-OCV 2.
Example 2
The ternary soft package lithium ion battery is prepared through the following steps, and self-discharge evaluation is carried out after formation:
(1) preparing a ternary soft package lithium ion battery:
(1.1) preparing an electrolyte: adding lithium hexafluorophosphate into ethylene carbonate to make the concentration of lithium hexafluorophosphate be 1 mol/L; then adding an electrolyte additive, wherein the using amount of the electrolyte additive is 5% of the total mass of the electrolyte, uniformly mixing until the solid is completely dissolved, and the structural formula of the electrolyte additive is as follows:
(1.2) preparing a positive pole piece: LiNi of nickel cobalt lithium manganate is mixed according to the ratio of 93:3:40.8Co0.1Mn0.1O2Dispersing PVDF and a conductive agent in N-methyl pyrrolidone to obtain positive electrode slurry; uniformly coating the positive electrode slurry on an aluminum foil, drying, rolling, slitting and punching to obtain a positive electrode plate;
(1.3) preparing a negative pole piece: dispersing artificial graphite, carboxymethyl cellulose and a conductive agent in water according to a ratio of 95:2:3, and uniformly stirring to obtain negative electrode slurry; uniformly coating the negative electrode slurry on a copper foil, drying, rolling, slitting and punching to obtain a negative electrode pole piece;
(1.4) preparing a separator: coating the ceramic on the two sides of the polypropylene layer, and drying to obtain the diaphragm;
(1.5) assembling a battery core: winding a sandwich structure consisting of the positive pole piece, the diaphragm and the negative pole piece, flattening the wound cylinder, welding a tab, packaging by using an aluminum-plastic film to obtain a dry cell, and drying in vacuum at 85 ℃;
(2) formation:
(2.1) normal temperature infiltration: after the battery core is injected with liquid, standing for 45 hours at the temperature of 25 ℃;
(2.2) one-time formation: sequentially using currents of 0.01C, 0.05C and 0.1C to charge the battery cell, and finally charging to 50% SOC (namely 3.8V) for the first time;
(2.3) primary degassing: firstly rolling the cell main body, and discharging internal gas into a gas bag, wherein the rolling pressure is 0.2 MPa; vacuumizing again, wherein the vacuum degree is 47Torr, and the vacuum maintaining time is 6 s;
(2.4) secondary formation: charging the cell to 100% SOC (i.e. 4.2V) using 0.3C current;
(2.5) high-temperature aging: standing at 35 deg.C for 45h, and cooling at room temperature;
(2.6) secondary degassing: firstly rolling the cell main body, and discharging internal gas into a gas bag, wherein the rolling pressure is 0.2 MPa; vacuumizing, wherein the vacuum degree is 10Torr, and the vacuum maintaining time is 10 s;
(3) capacity grading: charging to 4.2V by using a 0.3C constant current and constant voltage, then discharging to 2.7V by using a 0.3C constant current, and then charging to 4.2V by using a 0.3C constant current and constant voltage, and cutting off the current to 0.05C;
(4) self-discharge evaluation: after 22h at 25 ℃, the open circuit voltage was tested and reported as OCV 1: after the mixture is placed for 50 hours at the temperature of 25 ℃, the open-circuit voltage is tested and is marked as OCV 2; open circuit voltage decay OCV1-OCV 2.
Comparative example 1
The ternary soft package lithium ion battery is prepared through the following steps, and self-discharge evaluation is carried out after formation:
(1) preparing a ternary soft package lithium ion battery:
(1.1) preparing an electrolyte: adding lithium hexafluorophosphate into ethylene carbonate to make the concentration of lithium hexafluorophosphate be 1 mol/L;
(1.2) preparing a positive pole piece: LiNi of nickel cobalt lithium manganate is mixed according to the ratio of 93:3:40.8Co0.1Mn0.1O2Dispersing PVDF and a conductive agent in N-methyl pyrrolidone to obtain positive electrode slurry; uniformly coating the positive electrode slurry on an aluminum foil, drying, rolling, slitting and punching to obtain a positive electrode plate;
(1.3) preparing a negative pole piece: dispersing artificial graphite, carboxymethyl cellulose and a conductive agent in water according to a ratio of 95:2:3, and uniformly stirring to obtain negative electrode slurry; uniformly coating the negative electrode slurry on a copper foil, drying, rolling, slitting and punching to obtain a negative electrode pole piece;
(1.4) preparing a separator: coating the ceramic on the two sides of the polypropylene layer, and drying to obtain the diaphragm;
(1.5) assembling a battery core: winding a sandwich structure consisting of the positive pole piece, the diaphragm and the negative pole piece, flattening the wound cylinder, welding a tab, packaging by using an aluminum-plastic film to obtain a dry cell, and drying in vacuum at 85 ℃;
(2) formation:
(2.1) normal temperature infiltration: after the battery core is injected with liquid, standing for 45 hours at the temperature of 25 ℃;
(2.2) one-time formation: sequentially using currents of 0.02C and 0.2C to charge the battery cell, and finally charging to 50% SOC (namely 3.8V);
(2.3) primary degassing: firstly rolling the cell main body, and discharging internal gas into a gas bag, wherein the rolling pressure is 0.2 MPa; vacuumizing again, wherein the vacuum degree is 47Torr, and the vacuum maintaining time is 6 s;
(2.4) secondary formation: charging the cell to 100% SOC (i.e. 4.2V) using 0.3C current;
(2.5) high-temperature aging: standing at 35 deg.C for 45h, and cooling at room temperature;
(2.6) secondary degassing: firstly rolling the cell main body, and discharging internal gas into a gas bag, wherein the rolling pressure is 0.2 MPa; vacuumizing, wherein the vacuum degree is 10Torr, and the vacuum maintaining time is 10 s;
(3) capacity grading: charging to 4.2V by using a 0.3C constant current and constant voltage, then discharging to 2.7V by using a 0.3C constant current, and then charging to 4.2V by using a 0.3C constant current and constant voltage, and cutting off the current to 0.05C;
(4) self-discharge evaluation: after 22h at 25 ℃, the open circuit voltage was tested and reported as OCV 1: after the mixture is placed for 50 hours at the temperature of 25 ℃, the open-circuit voltage is tested and is marked as OCV 2; open circuit voltage decay OCV1-OCV 2.
Comparative example 2
The ternary soft package lithium ion battery is prepared through the following steps, and self-discharge evaluation is carried out after formation:
(1) preparing a ternary soft package lithium ion battery:
(1.1) preparing an electrolyte: adding lithium hexafluorophosphate into ethylene carbonate to make the concentration of lithium hexafluorophosphate be 1 mol/L;
(1.2) preparing a positive pole piece: LiNi of nickel cobalt lithium manganate is mixed according to the ratio of 93:3:40.8Co0.1Mn0.1O2Dispersing PVDF and a conductive agent in N-methyl pyrrolidone to obtain positive electrode slurry; uniformly coating the positive electrode slurry on an aluminum foil, drying, rolling, slitting and punching to obtain a positive electrode plate;
(1.3) preparing a negative pole piece: dispersing artificial graphite, carboxymethyl cellulose and a conductive agent in water according to a ratio of 95:2:3, and uniformly stirring to obtain negative electrode slurry; uniformly coating the negative electrode slurry on a copper foil, drying, rolling, slitting and punching to obtain a negative electrode pole piece;
(1.4) preparing a separator: coating the ceramic on the two sides of the polypropylene layer, and drying to obtain the diaphragm;
(1.5) assembling a battery core: winding a sandwich structure consisting of the positive pole piece, the diaphragm and the negative pole piece, flattening the wound cylinder, welding a tab, packaging by using an aluminum-plastic film to obtain a dry cell, and drying in vacuum at 85 ℃;
(2) formation:
(2.1) normal temperature infiltration: after the battery core is injected with liquid, standing for 45 hours at the temperature of 25 ℃;
(2.2) one-time formation: sequentially using currents of 0.01C, 0.05C and 0.1C to charge the battery cell, and finally charging to 50% SOC for the first time;
(2.3) primary degassing: firstly rolling the cell main body, and discharging internal gas into a gas bag, wherein the rolling pressure is 0.2 MPa; vacuumizing again, wherein the vacuum degree is 47Torr, and the vacuum maintaining time is 6 s;
(2.4) secondary formation: charging the battery cell to 70% SOC by using 0.3C current;
(2.5) high-temperature aging: standing at 35 deg.C for 24h, and cooling at room temperature;
(2.6) secondary degassing: firstly rolling the cell main body, and discharging internal gas into a gas bag, wherein the rolling pressure is 0.2 MPa; vacuumizing, wherein the vacuum degree is 10Torr, and the vacuum maintaining time is 10 s;
(3) capacity grading: charging to 4.2V by using a 0.3C constant current and constant voltage, then discharging to 2.7V by using a 0.3C constant current, and then charging to 4.2V by using a 0.3C constant current and constant voltage, and cutting off the current to 0.05C;
(4) self-discharge evaluation: after 22h at 25 ℃, the open circuit voltage was tested and reported as OCV 1: after the mixture is placed for 50 hours at the temperature of 25 ℃, the open-circuit voltage is tested and is marked as OCV 2; open circuit voltage decay OCV1-OCV 2.
Comparative example 3
The ternary soft package lithium ion battery is prepared through the following steps, and self-discharge evaluation is carried out after formation:
(1) preparing a ternary soft package lithium ion battery:
(1.1) preparing an electrolyte: adding lithium hexafluorophosphate into ethylene carbonate to make the concentration of lithium hexafluorophosphate be 1 mol/L; then adding an electrolyte additive MMDS (MMDS) with the dosage of 5 percent of the total mass of the electrolyte, and uniformly mixing until the solid is completely dissolved;
(1.2) preparing a positive pole piece: LiNi of nickel cobalt lithium manganate is mixed according to the ratio of 93:3:40.8Co0.1Mn0.1O2Dispersing PVDF and a conductive agent in N-methyl pyrrolidone to obtain positive electrode slurry; uniformly coating the positive electrode slurry on an aluminum foil, drying, rolling, slitting and punching to obtain a positive electrode plate;
(1.3) preparing a negative pole piece: dispersing artificial graphite, carboxymethyl cellulose and a conductive agent in water according to a ratio of 95:2:3, and uniformly stirring to obtain negative electrode slurry; uniformly coating the negative electrode slurry on a copper foil, drying, rolling, slitting and punching to obtain a negative electrode pole piece;
(1.4) preparing a separator: coating the ceramic on the two sides of the polypropylene layer, and drying to obtain the diaphragm;
(1.5) assembling a battery core: winding a sandwich structure consisting of the positive pole piece, the diaphragm and the negative pole piece, flattening the wound cylinder, welding a tab, packaging by using an aluminum-plastic film to obtain a dry cell, and drying in vacuum at 85 ℃;
(2) formation:
(2.1) normal temperature infiltration: after the battery core is injected with liquid, standing for 45 hours at the temperature of 25 ℃;
(2.2) one-time formation: sequentially using currents of 0.01C, 0.05C and 0.1C to charge the battery cell, and finally charging to 50% SOC (namely 3.8V) for the first time;
(2.3) primary degassing: firstly rolling the cell main body, and discharging internal gas into a gas bag, wherein the rolling pressure is 0.2 MPa; vacuumizing again, wherein the vacuum degree is 47Torr, and the vacuum maintaining time is 6 s;
(2.4) secondary formation: charging the cell to 100% SOC (i.e. 4.2V) using 0.3C current;
(2.5) high-temperature aging: standing at 35 deg.C for 45h, and cooling at room temperature;
(2.6) secondary degassing: firstly rolling the cell main body, and discharging internal gas into a gas bag, wherein the rolling pressure is 0.2 MPa; vacuumizing, wherein the vacuum degree is 10Torr, and the vacuum maintaining time is 10 s;
(3) capacity grading: charging to 4.2V by using a 0.3C constant current and constant voltage, then discharging to 2.7V by using a 0.3C constant current, and then charging to 4.2V by using a 0.3C constant current and constant voltage, and cutting off the current to 0.05C;
(4) self-discharge evaluation: after 22h at 25 ℃, the open circuit voltage was tested and reported as OCV 1: after the mixture is placed for 50 hours at the temperature of 25 ℃, the open-circuit voltage is tested and is marked as OCV 2; open circuit voltage decay OCV1-OCV 2.
The invention characterizes the self-discharge degree of the lithium ion battery by measuring the change of the open-circuit voltage in the standing process of the battery. OCV1, OCV2, and open circuit voltage decays (OCV1-OCV2) measured in examples 1-2 and comparative examples 1-3 are shown in Table 1.
TABLE 1
| OCV1/V | OCV2/V | Open circuit Voltage decay/mV | |
| Example 1 | 4.20894 | 4.20461 | 4.33 |
| Example 2 | 4.20583 | 4.20273 | 3.10 |
| Comparative example 1 | 4.20768 | 4.20428 | 5.40 |
| Comparative example 2 | 4.20396 | 4.19860 | 5.36 |
| Comparative example 3 | 4.20562 | 4.20177 | 3.85 |
Example 1 the first time composition was divided into 3 stages with currents of 0.01C, 0.05C and 0.1C, respectively; while comparative example 1 divided the first composition into 2 stages with currents of 0.02C and 0.2C, respectively. As seen from table 1, the open circuit voltage decay amplitude of example 1 was decreased by about 19.8% compared to comparative example 1, indicating that the present invention can reduce the self-discharge of the lithium ion battery by dividing the first formation into 3 stages and decreasing the current in each stage.
In example 1, the second formation charge was carried out to 100% SOC, and the high-temperature shelf life was 45 hours; in comparative example 2, the second formation charge was to 70% SOC, and the high temperature shelf life was 24 hours. From table 1, the open circuit voltage decay amplitude of example 1 decreased by about 19.2% compared to comparative example 2, indicating that the present invention can reduce the self-discharge of the lithium ion battery by charging the battery to full charge at the second formation and extending the high temperature shelf life.
In example 2, a novel electrolyte additive was added to the electrolyte of the battery in an amount of 5% by mass based on the total mass of the electrolyte, and the other conditions were the same as in example 1. From table 1, the open circuit voltage decay amplitude of example 2 decreased by about 36.1% compared to example 1, indicating that the self-discharge problem of the lithium ion battery can be effectively alleviated by adding the novel electrolyte additive of the present invention.
In comparative example 3, the electrolyte additive used was MMDS of the prior art, and the rest of the conditions were the same as in example 2. From table 1, the open circuit voltage decay amplitude of example 2 is about 19.5% less than that of comparative example 3, indicating that the novel electrolyte additive of the present invention can more effectively alleviate the self-discharge problem of the lithium ion battery compared to the electrolyte additive MMDS of the prior art.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. A formation method of a ternary soft package power lithium ion battery with a low self-discharge rate is characterized by comprising the following steps:
(1) normal temperature infiltration: after the battery cell is injected with liquid, standing for 40-48 h at the temperature of 22-28 ℃;
(2) the method comprises the following steps of (1) one-time formation: sequentially using currents of 0.01-0.03C, 0.04-0.06C and 0.08-0.1C to charge the battery cell, and finally charging to 40% -60% SOC for the first time;
(3) primary degassing: firstly rolling the cell main body, discharging internal gas, and then vacuumizing;
(4) carrying out secondary formation: charging the battery cell by using a current of 0.2-0.5C until the battery cell is charged to 100% SOC;
(5) and (3) high-temperature aging: standing at the temperature of 33-38 ℃ for 40-48 h, and then cooling at normal temperature;
(6) secondary degassing: and rolling the cell main body, discharging internal gas, and vacuumizing.
2. The formation method of the ternary soft-package power lithium ion battery with low self-discharge rate according to claim 1, characterized in that in the step (3), the rolling pressure is 0.2-0.3 MPa during rolling; and when vacuumizing, the vacuum degree is 25-47 Torr, and the time for keeping the vacuum is 5-8 s.
3. The formation method of the ternary soft-package power lithium ion battery with low self-discharge rate as claimed in claim 1, wherein in the step (6), the rolling pressure is 0.2-0.3 MPa during rolling; and when the vacuum is pumped, the vacuum degree is 5-15 Torr, and the time for keeping the vacuum is 10-15 s.
4. The ternary soft-package power lithium ion battery prepared by the formation method of any one of claims 1 to 3, which is characterized by comprising a positive electrode, a negative electrode, a diaphragm and an electrolyte; the electrolyte comprises an electrolyte additive, and the structural formula of the electrolyte additive is as follows:
wherein X is any one of the following cases:
a straight chain or branched chain alkyl group with 1-5 carbon atoms;
a linear or branched alkoxy group having 1 to 5 carbon atoms;
a straight or branched alkyl group in which some or all of the hydrogens are substituted with halogen atoms;
phenyl or substituted phenyl;
a carbonate group or a carbonate group substituted with a halogen atom;
a halogen atom;
a hydrogen atom.
5. The ternary soft-pack power lithium ion battery according to claim 4, wherein the electrolyte comprises a lithium salt and an organic solvent; the lithium salt is lithium hexafluorophosphate; the organic solvent is at least one of ethylene carbonate and dimethyl carbonate.
6. The ternary soft-packaged power lithium ion battery according to claim 4, wherein the amount of the electrolyte additive is 0.01-10% of the total mass of the electrolyte.
7. The ternary soft-packaged power lithium ion battery according to claim 5, wherein the concentration of the lithium salt is 0.5-1.3 mol/L.
8. The ternary soft-packaged power lithium ion battery according to claim 5, wherein the organic solvent accounts for 80-90% of the total mass of the electrolyte.
9. The ternary soft-pack power lithium ion battery of claim 4, wherein:
the positive electrode comprises a positive active material, and the positive active material is a nickel-cobalt-manganese synthetic material; and/or
The negative electrode comprises a negative electrode active material which is graphite; and/or
The diaphragm is a polypropylene composite diaphragm coated with ceramic.
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