CN113871737A - Lithium ion battery activation method containing lithium-rich manganese-based material and obtained lithium ion battery - Google Patents

Lithium ion battery activation method containing lithium-rich manganese-based material and obtained lithium ion battery Download PDF

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CN113871737A
CN113871737A CN202010617558.XA CN202010617558A CN113871737A CN 113871737 A CN113871737 A CN 113871737A CN 202010617558 A CN202010617558 A CN 202010617558A CN 113871737 A CN113871737 A CN 113871737A
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lithium
equal
less
based material
ion battery
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董彬彬
张振宇
张斌
陈一帆
张博怀
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Beijing WeLion New Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a lithium ion battery activation method containing a lithium-rich manganese-based material and an obtained lithium ion battery. The activation method can effectively activate the capacity rich in lithium and manganese and simultaneously can relieve the problem of gas generation. After the activation by the method, the lithium-rich manganese-based material can be charged and discharged at proper voltage, so that the performance of the lithium-rich manganese-based material can be effectively exerted, the problem that the lithium-rich manganese-based material cannot be practically used is solved, and the lithium-rich manganese-based material is industrially applied in a large scale.

Description

Lithium ion battery activation method containing lithium-rich manganese-based material and obtained lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery activation method containing a lithium-rich manganese-based material and an obtained lithium ion battery.
Background
With the higher and higher requirements of the market on the energy density of the lithium ion battery, and the positive electrode material as one of the main factors for limiting the energy density of the lithium ion battery, the development of the positive electrode material is more and more urgent. Currently, lithium ion battery positive electrode materials which are commercialized mainly comprise lithium iron phosphate, lithium manganate, ternary materials, lithium cobaltate and the like, wherein the theoretical specific capacities of the ternary materials and the lithium cobaltate are relatively high, and the development trends of the ternary materials and the lithium cobaltate are respectively in the directions of high nickel and high voltage. However, the cost control of the ternary material and the lithium cobaltate material is more and more urgent because of the relatively high cost of the raw materials. The lithium-rich manganese-based material has relatively high manganese content, and the metal manganese has very obvious price advantage compared with metal nickel and metal cobalt, so the raw material cost of the lithium-rich manganese-based material is relatively low.
The lithium-rich manganese-based material is widely concerned by researchers and enterprises at home and abroad due to the ultrahigh theoretical specific capacity. The lithium-rich manganese-based material has the problems of low efficiency, poor rate capability, voltage attenuation and the like for the first time, so that the lithium-rich manganese-based material cannot be industrially applied in late time. The capacity of the lithium-rich manganese-based material under the conventional low voltage is very small, and the ultrahigh capacity needs higher charge cut-off voltage (>4.5V vs Li/Li+) However, the battery system has various problems under high pressure, such as decomposition of the electrolyte, high-pressure oxygen evolution, structural collapse of the positive electrode material, and the like. The activation system for lithium-rich materials is particularly important.
CN103647115B was activated by high voltage (cutoff >4.4V) and then cycled at the cutoff of low voltage activation voltage. On one hand, when the activation voltage is low (such as 4.5V), the capacity of the lithium-rich manganese-based material cannot be completely activated, and when the activation voltage is high (such as 4.9V), the problem of violent oxygen release exists, and on the other hand, when the voltage for recycling is still high (such as 4.6V), the lithium-rich material is difficult to popularize and use due to instability under high pressure regardless of an electrolyte or the lithium-rich material.
The CN107959071B is activated by at least two low-voltage charge and discharge cycles and at least one high-voltage charge and discharge cycle, which can partially alleviate the problem of oxygen release, but still has the problem that the activation voltage may not activate the effective capacity of the lithium-rich manganese-based material due to low voltage (e.g. 4.4V), and also has the problem that the cut-off voltage is too high to effectively alleviate the voltage drop.
Therefore, the existing technical scheme still has defects, so that the lithium-rich manganese-based material is difficult to be applied in a large-scale industrialized mode.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for activating a lithium ion battery containing a lithium-rich manganese-based material and the lithium ion battery obtained by the method. The method can effectively exert the advantages of the lithium-rich manganese-based material, thereby promoting the large-scale use of the lithium-rich manganese-based material.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a method for activating a lithium ion battery containing a lithium-rich manganese-based material, which comprises the following steps:
(1) early activation: applying current I to a lithium ion battery containing a lithium-rich manganese-based material1Constant current charging is carried out, and the cut-off voltage is V1Then with a current I2Constant current discharge is carried out, and the cut-off voltage is V2Obtaining a battery after early activation; repeating the early-stage activation process for n times, wherein n is more than or equal to 1;
(2) and (3) later-stage activation: the battery after the early activation is applied with current I3Constant current charging is carried out, and the cut-off voltage is V3Then with a current I4Constant current discharge is carried out, and the cut-off voltage is V4(ii) a The V is1<V3(ii) a And repeating the later activation process for m times, wherein m is more than or equal to 1.
The process of repeating the previous activation for n times is as follows: using the parameters I selected by the invention1、I2、V1And V2At least one prior activation process is performed, exemplary being: 0.1C to 4.4V, 0.1C to 2V; then 0.15C was charged to 4.5V and 0.1C was discharged to 3V.
The process of repeatedly carrying out the later-stage activation for m times is as follows: using the parameters I selected by the invention3、I4、V3And V4Performing at least one post-sessionChemical processes, such as: 0.15C to 4.62V, 0.1C to 3V; then 0.15C is charged to 4.65V, 0.1C is discharged for 3V; finally, 0.15C was charged to 4.65V and 0.1C was discharged to 3.1V.
The early activation process can carry out preliminary activation, does not generate a large amount of gas, can effectively form a CEI film, stabilizes the surface structure of the material, and reduces gas generation and structural damage under higher voltage; the post-activation process can make most of Li2MnO3The structure has corresponding phase change, and the activation is more sufficient, so that the material can exert more capacity.
V of the invention1<V3，V1<V3The most excellent activation effect can be achieved by selecting the voltage. If V1Greater than or equal to V3Then V is1Large gas generation may occur due to excess, resulting in unstable surface structure, and V3Too small to allow a large fraction of Li2MnO3The structure is correspondingly changed in phase, thereby causing the problem of smaller capacity exertion.
The activation method can effectively activate the capacity rich in lithium and manganese and simultaneously can relieve the problem of gas generation. After the activation by the method, the lithium-rich manganese-based material can be charged and discharged at proper voltage, so that the performance of the lithium-rich manganese-based material can be effectively exerted, the problem that the lithium-rich manganese-based material cannot be practically used is solved, and the lithium-rich manganese-based material is industrially applied in a large scale.
Preferably, said V1≤V0<V3Said V is0It was 4.6V. + -. 50 mV.
The negative electrode material of the lithium ion battery containing the lithium-rich manganese-based material is not particularly limited, and all negative electrode materials can be applied to the invention, and can be selected from metallic lithium or graphite materials as an example. The cathode material can be selected from metallic lithium (when the metallic lithium is selected, the V is selected)04.6V ± 50mV), if other negative electrode materials are used in the battery, the cut-off voltage can be adjusted according to the actual application potential of other negative electrodes to lithium, for example, when the negative electrode material is a carbon material, V is04.55V +/-50 mV; when the negative electrode material is a silicon-based material, V04.55V +/-50 mV; when the negative electrode material is lithium titanate, V0The concentration was 3.05V. + -. 50 mV.
Preferably, step (1) is performed by I15C ≦ 5C (e.g., 0.001C, 0.002C, 0.005C, 0.01C, 0.05C, 0.08C, 0.1C, 0.2C, 0.3C, 0.4C, 0.5C, 0.6C, 0.7C, 0.8C, 0.9C, 1C, 2C, 3C, 4C, or 5C, etc.), preferably 0.002C ≦ I1≤2C。
Preferably, the 4.4V is less than or equal to V in the step (1)14.6V or less, for example, 4.42V, 4.45V, 4.48V, 4.5V, 4.52V, 4.55V or 4.58V, etc.
V is not less than 4.4V1≤4.6V，V1If the size is too large, large gas production can occur, so that the surface structure is unstable; v1Too small to effectively activate the corresponding structure, lower capacity exertion, or more activation is required, thereby lowering production efficiency.
Preferably, step (1) is performed by I25C ≦ 5C (e.g., 0.001C, 0.002C, 0.005C, 0.01C, 0.05C, 0.08C, 0.1C, 0.2C, 0.3C, 0.4C, 0.5C, 0.6C, 0.7C, 0.8C, 0.9C, 1C, 2C, 3C, 4C, or 5C, etc.), preferably 0.002C ≦ I2≤2C。
Preferably, 2.0 V.ltoreq.V in step (1)23.2V or less, e.g., 2.1V, 2.2V, 2.3V, 2.4V, 2.5V, 2.6V, 2.7V, 2.8V, 2.9V, 3.0V or 3.1V, etc.
Preferably, step (2) is performed by I35C ≦ 5C (e.g., 0.001C, 0.002C, 0.005C, 0.01C, 0.05C, 0.08C, 0.1C, 0.2C, 0.3C, 0.4C, 0.5C, 0.6C, 0.7C, 0.8C, 0.9C, 1C, 2C, 3C, 4C, or 5C, etc.), preferably 0.002C ≦ I3≤2C。
Preferably, 4.6V is adopted in the step (2)<V35.0V or less, e.g., 4.62V, 4.65V, 4.68V, 4.7V, 4.72V, 4.75V, 4.78V, 4.8V, 4.82V, 4.85V, 4.88V, 4.9V, 4.92V, 4.95V or 4.98V, etc.
The 4.6V is<V3≤5.0V，V3Too large because the lithium-rich material already exerts most of its capacity before 5V and the liquid electrolyte is more likely to decompose at higher voltages, resulting inThe finished battery fails; v3Too small to make most of Li2MnO3The structure is correspondingly changed in phase, thereby causing the problem of smaller capacity exertion.
Preferably, step (2) is performed by I45C ≦ 5C (e.g., 0.001C, 0.002C, 0.005C, 0.01C, 0.05C, 0.08C, 0.1C, 0.2C, 0.3C, 0.4C, 0.5C, 0.6C, 0.7C, 0.8C, 0.9C, 1C, 2C, 3C, 4C, or 5C, etc.), preferably 0.002C ≦ I4≤2C。
Preferably, 2.0 V.ltoreq.V in step (2)43.2V or less, e.g., 2.1V, 2.2V, 2.3V, 2.4V, 2.5V, 2.6V, 2.7V, 2.8V, 2.9V, 3.0V or 3.1V, etc.
Preferably, after the post-activation, a process of vacuumizing and sealing is further included.
Preferably, before and/or after the pre-activation, a process of vacuumizing and sealing is further included.
Preferably, in the lithium ion battery containing the lithium-rich manganese-based material, the positive electrode active material comprises the lithium-rich manganese-based material, and is preferably a mixed material of the lithium-rich manganese-based material and other positive electrode materials.
Preferably, the mass ratio of the lithium-rich manganese-based material in the positive electrode active material is 1 wt% to 100 wt%, such as 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt%, and the like.
Preferably, the lithium-rich manganese-based material has the chemical formula nLi2MnO3·(1-n)LiM’O2Wherein M' is one or more selected from Fe, Al, Co, Mn, Ni, Cr, Ti, Mo, Nb, Zr, Sn, V, Mg, Cu, Zn, B, Na, Ca and Ru, 0<n.ltoreq.1 (e.g. 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 etc.).
Preferably, the other cathode material has a chemical formula of LizFexMnyM”1-x-yPO4/C、LidNiaCobMncM”’1-a-b-cO2And LifMngM””2-gO4One or more of (a).
Wherein 0. ltoreq. x.ltoreq.1 (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, etc.), 0. ltoreq. y.ltoreq.1 (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, etc.), 1-x-y.ltoreq.0, 0.9. ltoreq. z.ltoreq.1.2 (e.g., 0.92, 0.95, 0.98, 1.0, 1.02, 1.05, 1.08, 1.1, 1.12, 1.15, or 1.18, etc.), 0. ltoreq. a.ltoreq.1 (e.0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9), 0. ltoreq. b.1 (e.1, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 0.1.1, 0.02, 0.1.1.9, 0.1.1, 0.1.1.1.05, 0.9, 0.1.1.9, 0.9, 0.1.1.1.1, 0.9, 0.1.1.9, 0.9, 0.1.1.1.9, 0.1.1.9, 0.1, 0.1.1, 0.1.1.1.1.1.1.1.9, 0.1.9, 0.1, 0.1.1, 0.1.1.1, 0.9, 0.1, 0.9, 0.1, 0.1.1, 0.1, 0.1.9, 0.9, 0.1, 0.9, etc.), etc., 0.9, etc., 0.9, 0.1.1.1.9, etc., 0.9, 0.1.1.1.9, 0.1, 0.9, 0.1, 0.1.1.9, 0.9, etc., 0.1.1, 0.9, 0.1.9, 0.9, etc., 0.9, etc., 0.1, 0.1.1.1.1.9, 0.9, 0.1.1.9, 0.9, 0.1.1, 0.9, etc.), 0.9, etc., 0.9, 0.1, 0.1.1, etc., 0.9, 0.1.9, etc., 0.1, 0.9, 0.1.1.1.1, 0.1.1.1.1.1.1, 0.1.1.1.1.9, etc., 0.1.1.1.1, etc., 0.9, etc., 0.1.9, etc., 0., 1.12, 1.15, or 1.18, etc.), 1.4 ≦ g ≦ 2 (e.g., 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, or 1.95, etc.); m' is one or more selected from Al, Co, Mn, Ni, Cr, Ti, V, Mg, Cu, Zn, Na, Ca and Zr; m' is selected from one or more of B, Al, Co, Mn, Ni, Cr, Ti, V, Mg, Cu, Zn, Na, Ca and Zr; m "" is selected from one or more of Al, Co, Mn, Ni, Cr, Ti, V, Mg, Cu, Zn, Na, Ca and Zr.
Preferably, the other positive electrode material is one or more of lithium iron phosphate, lithium manganese iron phosphate, lithium cobalt oxide, lithium nickelate, lithium manganate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and lithium nickel manganese oxide.
Preferably, the lithium ion battery containing the lithium-rich manganese-based material comprises a liquid lithium ion battery, a mixed solid-liquid metal lithium battery, an all-solid lithium ion battery and an all-solid metal lithium battery.
As a preferred technical scheme, the method for activating the lithium ion battery containing the lithium-rich manganese-based material comprises the following steps of:
(1) early activation: applying current I to a lithium ion battery containing a lithium-rich manganese-based material1Constant current charging is carried out, and I is more than or equal to 0.002C12C or less and a cut-off voltage V1V is not less than 4.4V1Less than or equal to 4.6V, then applying current I2Performing constant current discharge, wherein I is more than or equal to 0.002C22C or less and a cut-off voltage V2The V is more than or equal to 2.0V2Less than or equal to 3.2V to obtain the battery after early activation; repeating the early-stage activation process for n times, wherein n is more than or equal to 1;
(2) and (3) later-stage activation: the battery after the early activation is applied with current I3Constant current charging is carried out, and I is more than or equal to 0.002C32C or less and a cut-off voltage V3Said 4.6V<V3Less than or equal to 5.0V, then applying current I4Performing constant current discharge, wherein I is more than or equal to 0.002C42C or less and a cut-off voltage V4The V is more than or equal to 2.0V4Less than or equal to 3.2V; and repeating the later activation process for m times, wherein m is more than or equal to 1.
The second purpose of the present invention is to provide a lithium ion battery containing a lithium-rich manganese-based material, which is obtained by the method described in the first purpose.
Preferably, the charge cut-off voltage of the lithium ion battery containing the lithium-rich manganese-based material is less than or equal to 4.5V, such as 4.2V, 4.25V, 4.3V, 4.35V, 4.4V or 4.45V, and the like.
Compared with the prior art, the invention has the following beneficial effects:
the activation method can effectively activate the capacity rich in lithium and manganese and simultaneously can relieve the problem of gas generation. After the activation by the method, the lithium-rich manganese-based material can be charged and discharged at proper voltage, so that the performance of the lithium-rich manganese-based material can be effectively exerted, the problem that the lithium-rich manganese-based material cannot be practically used is solved, and the lithium-rich manganese-based material is industrially applied in a large scale.
Drawings
Fig. 1 is a graph comparing the cycle performance of cells after activation according to example 1 of the present invention and comparative example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A method for activating a lithium ion battery containing a lithium-rich manganese-based material comprises the following steps:
in the lithium ion battery containing the lithium-rich manganese-based material, the positive active material in the positive plate is 0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2Positive electrode active material in the positive electrode sheet: conductive agent SP: preparing a 2032 button cell by using a binder PVDF with a mass ratio of 90:5:5 and a negative electrode of a lithium sheet;
(1) early activation: applying current I to a lithium ion battery containing a lithium-rich manganese-based material1Constant current charging is carried out at 0.05C, and the cut-off voltage V1Standing at 4.5V for 30 min; then with a current I2Constant current discharge at 0.05C, cut-off voltage V2The voltage is 2.0V, and the battery after early activation is obtained;
(2) and (3) later-stage activation: the battery after the early activation is applied with current I3Constant current charging is carried out at 0.05C, and the cut-off voltage V3Standing for 30min at 4.7V; then with a current I4Constant current discharge at 0.05C, cut-off voltage V4It was 2.0V.
The electrochemical performance of the activated battery of this embodiment was tested, and the specific test method was as follows: testing the discharge specific capacity under the voltage range of 2.8-4.3V and 0.1C/0.1C (0.1C charging and 0.1C discharging); the voltage range is 2.8-4.3V, and the results of 100-cycle capacity retention rate of 1C/1C (1C charging and 1C discharging) tests are shown in Table 1.
Example 2
A method for activating a lithium ion battery containing a lithium-rich manganese-based material comprises the following steps:
in the lithium ion battery containing the lithium-rich manganese-based material, the positive active material in the positive plate is 70 wt% of LiMn2O4And 30 wt% of 0.5Li2MnO3·0.5LiNi0.5Mn0.5O2Lithium-rich material, positive active material in positive plate: conductive agent SP: preparing a 2032 button cell by using a binder PVDF with a mass ratio of 90:5:5 and a negative electrode of a lithium sheet;
(1) early activation: applying current I to a lithium ion battery containing a lithium-rich manganese-based material1Constant current charging is carried out at 0.002C, and the cut-off voltage V1Standing for 30min at 4.6V; then with a current I2Constant current discharge is performed at 0.002C, and the cut-off voltage V is2The voltage is 3.2V, and the battery after early activation is obtained;
(2) and (3) later-stage activation: the battery after the early activation is applied with current I3Constant current charging is carried out at 0.002C, and the cut-off voltage V3Standing for 30min at 5V; then with a current I4Constant current discharge is performed at 0.002C, and the cut-off voltage V is4It was 3.2V.
The electrochemical performance of the activated battery of this embodiment was tested, and the specific test method was as follows: testing the discharge specific capacity under the voltage range of 3.0-4.25V and 0.1C/0.1C (0.1C charging and 0.1C discharging); the voltage range is 3.0-4.25V, and the results of the 100-cycle capacity retention rate of 1C/1C (1C charging and 1C discharging) tests are shown in Table 1.
Example 3
A method for activating a lithium ion battery containing a lithium-rich manganese-based material comprises the following steps:
in the lithium ion battery containing the lithium-rich manganese-based material, the positive active material in the positive plate is 80 wt% of LiNi0.6Co0.2Mn0.2O2And 20 wt% of 0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2Lithium-rich material, positive active material in positive plate: conductive agent SP: preparing a 2032 button cell by using a binder PVDF with a mass ratio of 90:5:5 and a negative electrode of a lithium sheet;
(1) early activation: applying current I to a lithium ion battery containing a lithium-rich manganese-based material1Constant current charging for 2C, cut-off voltage V1Standing at 4.4V for 30 min; then with a current I2Constant current discharge for 2C, cut-off voltage V2The voltage is 2.1V, and a battery after early activation is obtained;
(2) and (3) later-stage activation: the battery after the early activation is applied with current I3Constant current charging for 2C, cut-off voltage V3Standing at 4.8V for 30 min; then with a current I4Constant current discharge for 2C, cut-off voltage V4It was 2.1V.
The test method, test parameters, and conditions of this example were the same as those of example 1.
Example 4
The difference from example 1 is that V1It was 4.3V.
The test method, test parameters, and conditions of this example were the same as those of example 1.
Example 5
The difference from example 1 is that V3It was 5.1V.
The test method, test parameters, and conditions of this example were the same as those of example 1.
Example 6
The lithium ion battery containing the lithium-rich manganese-based material adopted in the present example is the same as that of example 1;
(1) early activation: applying current I to a lithium ion battery containing a lithium-rich manganese-based material11Constant current charging is carried out at 0.05C, and the cut-off voltage V11Standing at 4.5V for 30 min; with a current I21Constant current discharge at 0.05C, cut-off voltage V21Is 2.0V;
then with a current I12Constant current charging is carried out at 0.1C, and the cut-off voltage V12Standing at 4.55V for 30 min; with a current I22Constant current discharge at 0.1 deg.C, cut-off voltage V22The voltage is 2.0V, and the battery after early activation is obtained;
(2) and (3) later-stage activation: the battery after the early activation is applied with current I3Constant current charging is carried out at 0.05C, and the cut-off voltage V3Standing for 30min at 4.7V; then with a current I4Constant current discharge at 0.05C, cut-off voltage V4At 2.0V, it was reactivated 2 times in the same activation procedure.
The test method, test parameters, and conditions of this example were the same as those of example 1.
Comparative example 1
The difference from the embodiment 1 is that the voltage range of the specific discharge capacity and the 100-cycle capacity retention ratio test is 2.8-4.7V.
Comparative example 2
The lithium ion battery containing the lithium-rich manganese-based material that was not activated in example 1 was used (no pre-activation and post-activation were performed).
This comparative example was identical to example 1 in the test method, test parameters, and conditions.
Comparative example 3
The difference from example 1 is that V1It was 4.7V.
This comparative example was identical to example 1 in the test method, test parameters, and conditions.
Comparative example 4
The difference from example 1 is that V3It was 4.5V.
This comparative example was identical to example 1 in the test method, test parameters, and conditions.
Comparative example 5
The difference from example 1 is that the post-activation process was not performed, i.e., the test was performed using the battery after the pre-activation.
This comparative example was identical to example 1 in the test method, test parameters, and conditions.
Comparative example 6
The difference from example 1 is that no previous activation process was performed.
This comparative example was identical to example 1 in the test method, test parameters, and conditions.
TABLE 1
Figure BDA0002561896290000111
Figure BDA0002561896290000121
As is clear from comparison between example 1 and example 4, when the early activation voltage is greater than 4.4V, the lithium-rich material can be activated more favorably, and a higher capacity can be obtained. As is clear from comparison between example 1 and example 5, when the activation voltage is too high in the later stage (5.1V), the electrolyte is greatly affected, and the cyclability is deteriorated.
As can be seen by comparing example 1 with comparative examples 1-2 in Table 1, the initial specific capacity of example 1 is lower than that of comparative example 1, but much higher than that of comparative example 2; also in conjunction with fig. 1, it can be seen that the cycle performance of example 1 is much better than that of comparative example 1. The battery performance in example 1 is exerted, and advantages in terms of capacity, cycle, and the like are integrated, and it can be put to practical use.
It is understood from comparison between example 1 and comparative example 3 that the first activation voltage is too high, which causes instability of the surface structure and affects the performance of the cycle performance. As can be seen from comparison between example 1 and comparative example 4, when the activation voltage at the later stage is too low, it is difficult to effectively activate the lithium-rich structure, resulting in a lower specific capacity.
As is clear from comparison of example 1 with comparative example 5, it is difficult to effectively activate the lithium-rich structure without post-activation, and the capacity is low. It can be seen from the comparison of example 1 with comparative example 6 that, without prior activation, on the one hand, lithium-rich structures cannot be activated better, and on the other hand, direct high-pressure activation may cause instability of the surface structure, thereby affecting the cycle performance.
The comparison between the example 1 and the example 3 also shows that the capacity exertion of the lithium-rich manganese-based material under low pressure can be much higher than that of the common ternary material under the same test voltage, and the lithium-rich manganese-based material has important significance for the practical application of the lithium-rich manganese base.
Example 7
A method for activating a lithium ion battery containing a lithium-rich manganese-based material comprises the following steps:
in the lithium ion battery containing the lithium-rich manganese-based material, the positive active material in the positive plate is LiNi of 90%0.5Co0.2Mn0.3O2And 10% of 0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2The lithium-rich material is used, and graphite is used as a negative active material in the negative plate to assemble a soft package battery cell of about 2 Ah;
(1) early activation: applying current I to a lithium ion battery containing a lithium-rich manganese-based material1Constant current charging is carried out at 0.05C, and the cut-off voltage V1Standing at 4.5V for 30 min; then with a current I2Constant current discharge at 0.05C, cut-off voltage V2Carrying out primary vacuumizing packaging at 2.8V to obtain a battery activated at the early stage;
(2) and (3) later-stage activation: the battery after the early activation is applied with current I3Constant current charging is carried out at 0.1C, and the cut-off voltage V3Standing at 4.75V for 30 min; then with a current I4Constant current discharge at 0.1 deg.C, cut-off voltage V4It was 2.8V. And vacuumizing and packaging the activated lithium ion battery to obtain the final battery.
Testing the final battery under the voltage range of 2.8-4.3V and 0.1C/0.1C (0.1C charging and 0.1C discharging) to obtain the capacity; then, the cycle capacity retention ratio of 200 weeks is tested in a voltage range of 2.8-4.3V and 1C/1C (1C charging and 1C discharging), and the results are shown in Table 2.
Example 8
The difference from example 7 is that the active material was changed to 0.5Li2MnO3·0.5LiNi1/3Co1/3Mn1/3O2A lithium rich material.
The test method, test parameters, and conditions in this example were the same as those in example 7.
Comparative example 7
The lithium ion battery containing the lithium-rich manganese-based material adopted in the present example is the same as in example 7;
the general activation method is adopted: the lithium ion battery containing the lithium-rich manganese-based material is charged with current I1Constant current charging is carried out at 0.05C, and the cut-off voltage V1Standing for 30min at 4.3V; then with a current I2Constant current discharge at 0.05C, cut-off voltage V2Carrying out primary vacuumizing packaging at 2.8V to obtain a battery;
this comparative example was identical to example 7 in the test method, test parameters, and conditions.
Comparative example 8
The lithium ion battery containing the lithium-rich manganese-based material adopted in the present example is the same as that of example 8;
the general activation method is adopted: the lithium ion battery containing the lithium-rich manganese-based material is charged with current I1Is 0.05C is charged with constant current, and the cut-off voltage V is1Standing for 30min at 4.3V; then with a current I2Constant current discharge at 0.05C, cut-off voltage V2Carrying out primary vacuumizing packaging at 2.8V to obtain a battery;
this comparative example was identical to example 7 in the test method, test parameters, and conditions.
Comparative example 9
The lithium ion battery containing the lithium-rich manganese-based material adopted in the present example is the same as that of example 8;
the general activation method is adopted: the lithium ion battery containing the lithium-rich manganese-based material is charged with current I1Constant current charging is carried out at 0.05C, and the cut-off voltage V1Standing for 30min at 4.7V; then with a current I2Constant current discharge at 0.05C, cut-off voltage V2Carrying out primary vacuumizing packaging at 2.8V to obtain a battery;
testing the finally obtained battery under the voltage range of 2.8-4.7V and 0.1C/0.1C (0.1C charging and 0.1C discharging) to obtain the capacity; then, the cycle capacity retention ratio of 200 weeks was tested in a voltage range of 2.8-4.7V and 1C/1C (1C charge, 1C discharge), and the results are shown in Table 2.
Comparative example 10
The difference from example 8 is that the test method is different: testing the final battery under the voltage range of 2.8-4.7V and 0.1C/0.1C (0.1C charging and 0.1C discharging) to obtain the capacity; then, the cycle capacity retention ratio of 200 weeks was tested in a voltage range of 2.8-4.7V and 1C/1C (1C charge, 1C discharge), and the results are shown in Table 2.
TABLE 2
Sample (I) Capacity (Ah) 200-week cycle Performance (%) Condition of flatulence
Example 7 2.04 92 Is free of
Example 8 2.06 88 Is free of
Comparative example 7 1.98 92 Is free of
Comparative example 8 1.22 91 Is free of
Comparative example 9 2.40 9 Is provided with
Comparative example 10 2.42 11 Is provided with
From the comparison of example 7 with comparative example 7, and the comparison of example 8 with comparative example 8, it is understood that the capacity of the lithium-rich manganese-based material can be more effectively activated using the activation method of the present invention, thereby allowing the higher capacity to be exerted as a whole.
It is understood from the comparison between example 8 and comparative examples 9 to 10 that the voltage applied in the test is too high, and although more capacity can be exerted, the cycle performance is seriously reduced due to serious problems such as serious gas generation, decomposition of the electrolyte, and destruction of the material structure, and thus the practical application is difficult.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A method for activating a lithium ion battery containing a lithium-rich manganese-based material is characterized by comprising the following steps:
(1) early activation: applying current I to a lithium ion battery containing a lithium-rich manganese-based material1Constant current charging is carried out, and the cut-off voltage is V1Then with a current I2Constant current discharge is carried out, and the cut-off voltage is V2Obtaining a battery after early activation; repeating the early-stage activation process for n times, wherein n is more than or equal to 1;
(2) and (3) later-stage activation: the battery after the early activation is applied with current I3Constant current charging is carried out, and the cut-off voltage is V3Then with a current I4Constant current discharge is carried out, and the cut-off voltage is V4(ii) a The V is1<V3(ii) a And repeating the later activation process for m times, wherein m is more than or equal to 1.
2. The method of claim 1, wherein V is1≤V0<V3Said V is04.6V +/-50 mV;
preferably, step (1) is performed by I15C or less, preferably 0.002C or less I1≤2C；
Preferably, the 4.4V is less than or equal to V in the step (1)1≤4.6V。
3. The method of claim 1 or 2, wherein step (1) is step (1) or step (2) is step (ii)25C or less, preferably 0.002C or less I2≤2C；
Preferably, 2.0 V.ltoreq.V in step (1)2≤3.2V。
4. The method of any one of claims 1-3, wherein step (2) provides for I35C or less, preferably 0.002C or less I3≤2C；
Preferably, 4.6V is adopted in the step (2)<V3≤5.0V。
5. The method of any one of claims 1-4, wherein step (2) provides for I45C or less, preferably 0.002C or less I4≤2C；
Preferably, 2.0 V.ltoreq.V in step (2)4≤3.2V。
6. The method according to any one of claims 1 to 5, wherein the post-activation is followed by a vacuum sealing process;
preferably, before and/or after the pre-activation, a process of vacuumizing and sealing is further included.
7. The method according to any one of claims 1 to 6, wherein in the lithium ion battery containing the lithium-rich manganese-based material, the positive electrode active material comprises the lithium-rich manganese-based material, preferably a mixed material of the lithium-rich manganese-based material and other positive electrode materials;
preferably, in the positive active material, the mass ratio of the lithium-rich manganese-based material is 1 wt% to 100 wt%;
preferably, the lithium-rich manganese-based material has the chemical formula nLi2MnO3·(1-n)LiM’O2Wherein M' is selected from Fe, Al, Co, Mn, NiOne or more of Cr, Ti, Mo, Nb, Zr, Sn, V, Mg, Cu, Zn, B, Na, Ca and Ru, 0<n≤1；
Preferably, the other cathode material has a chemical formula of LizFexMnyM”1-x-yPO4/C、LidNiaCobMncM”’1-a-b-cO2And LifMngM””2-gO4One or more of;
wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, 1-x-y is more than or equal to 0.9 and less than or equal to 1, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, 1-a-b-c is more than or equal to 0, d is more than or equal to 0.9 and less than or equal to 1.2, f is more than or equal to 0.9 and less than or equal to 1.2, and g is more than or equal to 1.4 and less than or equal to 2; m' is one or more selected from Al, Co, Mn, Ni, Cr, Ti, V, Mg, Cu, Zn, Na, Ca and Zr; m' is selected from one or more of B, Al, Co, Mn, Ni, Cr, Ti, V, Mg, Cu, Zn, Na, Ca and Zr; m "" is selected from one or more of Al, Co, Mn, Ni, Cr, Ti, V, Mg, Cu, Zn, Na, Ca and Zr;
preferably, the other positive electrode material is one or more of lithium iron phosphate, lithium manganese iron phosphate, lithium cobalt oxide, lithium nickelate, lithium manganate, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminate and lithium nickel manganese oxide.
8. The method of any one of claims 1-7, wherein the lithium ion battery comprising the lithium-rich manganese-based material comprises a liquid lithium ion battery, a hybrid solid-liquid lithium metal battery, an all solid-state lithium ion battery, and an all solid-state lithium metal battery.
9. Method according to one of claims 1 to 8, characterized in that the method comprises the following steps:
(1) early activation: applying current I to a lithium ion battery containing a lithium-rich manganese-based material1Constant current charging is carried out, and I is more than or equal to 0.002C12C or less and a cut-off voltage V1V is not less than 4.4V1Less than or equal to 4.6V, then applying current I2Performing constant current discharge, wherein I is more than or equal to 0.002C22C or less and a cut-off voltage V2The V is more than or equal to 2.0V2Less than or equal to 3.2V to obtain the battery after early activation; repeating the early-stage activation process for n times, wherein n is more than or equal to 1;
(2) and (3) later-stage activation: the battery after the early activation is applied with current I3Constant current charging is carried out, and I is more than or equal to 0.002C32C or less and a cut-off voltage V3Said 4.6V<V3Less than or equal to 5.0V, then applying current I4Performing constant current discharge, wherein I is more than or equal to 0.002C42C or less and a cut-off voltage V4The V is more than or equal to 2.0V4Less than or equal to 3.2V; and repeating the later activation process for m times, wherein m is more than or equal to 1.
10. A lithium ion battery comprising a lithium-rich manganese-based material, wherein the lithium ion battery is obtained by the method of any one of claims 1 to 9;
preferably, the charge cut-off voltage of the lithium ion battery containing the lithium-rich manganese-based material is less than or equal to 4.5V.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114552037A (en) * 2022-02-21 2022-05-27 江西理工大学 Formation method of lithium ion battery with positive electrode made of lithium-rich manganese material
CN115275407A (en) * 2022-09-30 2022-11-01 北京金羽新材科技有限公司 Charging method of nickel-zinc battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103326069A (en) * 2012-03-20 2013-09-25 北汽福田汽车股份有限公司 Method for forming lithium manganese power cells
CN104319422A (en) * 2014-10-10 2015-01-28 奇瑞汽车股份有限公司 Method for improving cycling stability of lithium-manganese lithium ion battery
CN107959071A (en) * 2017-11-15 2018-04-24 国联汽车动力电池研究院有限责任公司 A kind of lithium ion battery and its chemical synthesizing method
CN108232311A (en) * 2017-12-20 2018-06-29 国联汽车动力电池研究院有限责任公司 A kind of chemical synthesizing method of lithium rechargeable battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103326069A (en) * 2012-03-20 2013-09-25 北汽福田汽车股份有限公司 Method for forming lithium manganese power cells
CN104319422A (en) * 2014-10-10 2015-01-28 奇瑞汽车股份有限公司 Method for improving cycling stability of lithium-manganese lithium ion battery
CN107959071A (en) * 2017-11-15 2018-04-24 国联汽车动力电池研究院有限责任公司 A kind of lithium ion battery and its chemical synthesizing method
CN108232311A (en) * 2017-12-20 2018-06-29 国联汽车动力电池研究院有限责任公司 A kind of chemical synthesizing method of lithium rechargeable battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114552037A (en) * 2022-02-21 2022-05-27 江西理工大学 Formation method of lithium ion battery with positive electrode made of lithium-rich manganese material
CN115275407A (en) * 2022-09-30 2022-11-01 北京金羽新材科技有限公司 Charging method of nickel-zinc battery
CN115275407B (en) * 2022-09-30 2022-12-20 北京金羽新材科技有限公司 Charging method of nickel-zinc battery

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