CN111785910A - Method for determining liquid injection amount of lithium ion battery - Google Patents

Method for determining liquid injection amount of lithium ion battery Download PDF

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CN111785910A
CN111785910A CN202010803502.3A CN202010803502A CN111785910A CN 111785910 A CN111785910 A CN 111785910A CN 202010803502 A CN202010803502 A CN 202010803502A CN 111785910 A CN111785910 A CN 111785910A
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liquid
amount
battery
electrolyte
determining
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CN111785910B (en
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暴旭
魏怡
郑彦俊
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Tianjin EV Energies Co Ltd
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Tianjin EV Energies Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44Methods for charging or discharging
    • H01M10/446Initial charging measures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/10Batteries in stationary systems, e.g. emergency power source in plant
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/20Batteries in motive systems, e.g. vehicle, ship, plane
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/30Batteries in portable systems, e.g. mobile phone, laptop
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Filling, Topping-Up Batteries (AREA)

Abstract

The invention provides a method for determining the injection amount of a lithium ion battery, which comprises the steps of weighing the mass of a battery cell without injection to obtain M0(ii) a Injecting excessive electrolyte into the battery core; disassembling the battery core after formation, pouring out the redundant electrolyte, weighing the mass of the core package, and recording the mass as M2Weighing the mass of the disassembled parts except the core bag, and recording as M3(ii) a Calculating the amount of purified liquid C ═ M2+M3‑M0(ii) a Taking a plurality of gradient liquid injection amounts upwards and downwards according to the value of the net liquid amount; respectively injecting a plurality of gradient electrolytes into a plurality of battery cores which are not injected with liquid, disassembling the battery cores after formation, and respectively recording the free liquid amount of the battery cores; and drawing by taking the liquid injection amount as a horizontal coordinate and the free liquid amount as a vertical coordinate, and determining an inflection point of the stable rising of the free liquid amount after connecting a line, wherein the liquid injection amount corresponding to the inflection point is the optimal liquid injection amount. Book (I)The method for determining the injection amount of the lithium ion battery is not limited by a battery system and is suitable for determining the injection amounts of all liquid electrolyte batteries.

Description

Method for determining liquid injection amount of lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a method for determining initial liquid injection amount of a lithium ion battery.
Background
Since the lithium ion battery is used in commercial applications, the lithium ion battery has a wide range of applications, is a reliable energy guarantee for many portable electronic products, can also be used as an energy storage device, and is also rapidly popularized in recent years in power battery automobiles. The lithium ion battery is a part of the technological progress of human beings and is important, and the lithium ion battery makes an important contribution to the human remote energy scheme.
The lithium ion battery can be divided into three major categories, namely liquid, gel and solid according to the type of the electrolyte, wherein the application scene of the liquid electrolyte is the most extensive. In the battery, the electrolyte is an important medium for transporting lithium ions, and is a bridge between the porous electrode of the positive electrode and the porous electrode of the negative electrode, so the usage amount of the electrolyte is a very important design parameter. Particularly for a soft package battery, when the electrolyte is very little, the electrolyte transmission channel is reduced, which easily causes the battery performance deterioration, but if the electrolyte is very much, the electrolyte that is dissociated between the pole pieces is too much, which causes the battery performance deterioration. The design of the amount of the electrolyte solution is very important.
In the prior art, the method for determining the optimal injection amount can be roughly divided into two methods, one method is to calculate the injection quality of the electrolyte by using a method for calculating the porosity of a pole piece and the porosity of a diaphragm and combining the density of the electrolyte. However, the method has the disadvantages that the actual calculated liquid amount can not necessarily support the actual battery circulation by neglecting the microscopic change of the expanded hole of the negative pole piece in the actual process; the other method is that an empirical value is used to estimate a liquid injection amount, and then the liquid injection amount with gradient change is used to test the yield, residual liquid amount and circulation performance of the battery to judge the liquid injection amount. The method has the disadvantages that the empirical value of a conventional battery system can be used, but the empirical value is probably inaccurate and greatly different from the actual value when a battery is made of a new material, and the process is limited by factory buildings and production line equipment on a given factory production line and cannot be adjusted too much because the material characteristics of the new material are completely different from the existing materials, such as carbon silicon, graphene and the like, and the pore volume is changed greatly due to the large specific surface area.
Disclosure of Invention
In view of the above, in order to solve the above problems, the present invention provides a method for determining an initial injection amount of a lithium ion battery, which is applicable to determination of injection amounts of all liquid electrolytes in batteries without being limited by a battery system.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for determining the initial liquid injection amount of a lithium ion battery comprises the following steps: (1) weighing the quality of the battery cell without liquid injection to obtain M0(ii) a (2) Injecting excessive electrolyte into the battery core which is not injected with the electrolyte; (3) disassembling the battery core after formation, pouring out redundant electrolyte, weighing the mass of the core package, and recording the mass as M2Weighing the mass of the disassembled parts except the core bag, and recording as M3(ii) a (4) Calculating the amount of purified liquid C ═ M2+M3-M0And the net liquid amount is the initial liquid injection amount.
Further, the mass of the excess electrolyte in the step (2) is recorded as M1,M1=2×V1×ρ1Where V1 is the pore volume, ρ1Is the electrolyte density.
Further, the pore volume is obtained by calculating the porosity of the pole piece and the diaphragm.
A method for determining the liquid injection amount of a lithium ion battery comprises the following steps:
(1) weighing the quality of the battery cell without liquid injection to obtain M0
(2) Injecting excessive electrolyte into the battery core which is not injected with the electrolyte; the mass of excess electrolyte is recorded as M1,M1The mass of the electrolyte can be 2 times of the pore volume, and the pore volume can be obtained by calculating the porosity of the pole piece and the diaphragm;
(3) disassembling the battery core after formation, pouring out redundant electrolyte, weighing the mass of the core package, and recording the mass as M2Weighing the mass of the disassembled parts except the core bag, and recording as M3(ii) a Wherein the technological conditions of the formation are the prior art and can be determined according to actual conditions;
(4) calculating the amount of purified liquid C ═ M2+M3-M0
(5) Performing gradient test, taking multiple gradient injection amounts upward and downward according to the value of the net liquid amount C, and respectively recording as C-n……C-2、C-1、C、C1、C2……Cn
(6) Respectively injecting the obtained injection quantities of the gradients into a plurality of battery cores which are not injected with liquid, disassembling the battery cores after formation, and recording the free liquid quantity of the battery cores as B-n……B-2、B-1、B、B1、B2……Bn
(7) And drawing a scatter diagram by taking the liquid injection amount as a horizontal coordinate and the free liquid amount as a vertical coordinate, determining an inflection point of the stable rising of the free liquid amount after connecting the lines, wherein the liquid injection amount corresponding to the inflection point is the optimal liquid injection amount.
Further, the variation of each gradient in the step (5) is 0.5-4% of the net liquid amount.
Further, the variation of each gradient in the step (5) is 1.8% of the net liquid amount.
Further, in the step (5), 3 gradients of liquid injection amounts are respectively taken up upwards and downwards according to the value of the net liquid amount C, and are recorded as C-3、C-2、C-1、C、C1、C2、C3
Use of a method for determining the charge capacity of a lithium ion battery, the use of the method in a pouch battery.
Compared with the prior art, the method for determining the liquid injection amount of the lithium ion battery has the following advantages:
(1) according to the method for determining the injection amount of the lithium ion battery, under the condition that a system is unknown, the initial electrolyte quality (net liquid amount) required by the battery of the system can be actually measured through a testing means, then a gradient experiment is carried out, and the optimal injection amount is determined by utilizing the relation between the free liquid amount and the injection amount, so that compared with the existing method, the obtained data is quicker and more intuitive, and the operation is simpler;
(2) the initial liquid injection amount is determined by actually manufacturing the battery core and obtaining the maximum liquid absorption amount of the system by a pre-charging method, namely the quality of electrolyte which can be absorbed by the battery in a full-charge state.
Drawings
FIG. 1 is a diagram illustrating the linear relationship between different injection amounts and free liquid amounts in the method for determining the injection amount of a lithium ion battery according to the present invention;
FIG. 2 is a graph showing the linear relationship between different injection amounts and free liquid amounts in example 1 of the present invention;
FIG. 3 is a graph showing cycle data at different injection amounts in example 1 of the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
A method for determining the liquid injection amount of a lithium ion battery comprises the following steps:
(1) preparing an electric core, weighing the mass of the electric core without being injected with liquid to obtain M0
(2) Injecting excessive electrolyte into the battery core which is not injected with the electrolyte; the mass of excess electrolyte is recorded as M1,M1Mass of electrolyte in 2 times pore volume, i.e. M1=2×V1×ρ1Where V1 is the pore volume, ρ1The pore volume can be calculated by the porosity of the pole piece and the diaphragm as the density of the electrolyte;
(3) standing at normal temperature for 1 day at high temperature, pre-charging for 12h, and formingThen disassembling the battery core, pouring out the redundant electrolyte, weighing the mass of the core package, and recording as M2Weighing the mass of the disassembled parts except the core bag, and recording as M3
(4) Calculating the net liquid amount (initial liquid amount) C ═ M2+M3-M0
(5) Performing gradient test, taking 3 gradient injection amounts upwards and downwards according to the value of the net liquid amount C, and respectively recording as C-3、C-2、C-1、C、C1、C2、C3Wherein the amount of change in each gradient is 1.8% of the net liquid amount;
(6) designing 7-gradient injection amount tests, and respectively injecting liquid into the cells which are not injected with the injection amount of C-3、C-2、C-1、C、C1、C2、C3Disassembling the electric core after formation, and recording the free liquid amount of the electric core as B-n……B-2、B-1、B、B1、B2……Bn(see table 1);
TABLE 1
Experiment number Amount of liquid injected Amount of free liquid
C-3 C-3*1.8%*C B-3
C-2 C-2*1.8%*C B-2
C-1 C-1*1.8%*C B-1
C C B
C1 C+1*1.8%*C B1
C2 C+2*1.8%*C B2
C3 C+3*1.8%*C B3
(7) And (3) drawing a scatter diagram by taking the liquid injection amount as an abscissa and the free liquid amount as an ordinate, determining an inflection point where the free liquid amount stably rises after connecting the lines, wherein the liquid injection amount corresponding to the inflection point is the optimal liquid injection amount (as shown in fig. 1, the third point is the inflection point, and the liquid injection amount corresponding to the inflection point is the optimal liquid injection amount).
Example 1
The method for determining the liquid injection amount of the lithium ion battery comprises the following steps:
(1) preparing an electric core:
a. establishing a continuous structure between the manufactured negative pole piece (total width 289mm (including a pole lug), material area width 265mm, thickness 160 mu m and length 3m) and two isolation membranes, wherein the membrane material is PP, and the two sides are coated with a ceramic layer and an adhesive layer, the thickness is 16 mu m, the width is 278mm and the length is 3.2 m;
b. cutting the positive pole piece into 29 positive pole pieces with the total width of 278mm (containing pole lugs), the width of a material area of 255mm, the thickness of 130 mu m and the height of 95 mm;
c. when the negative electrode and the diaphragm are folded in a Z shape, 1 positive electrode piece is put in and out of each folded layer, and the positive electrode piece, the negative electrode piece and the diaphragm are assembled together;
d. then, adhering the assembled core package firmly by using 10 adhesive tapes with the width of 7mm and the thickness of 30 microns;
e. welding a current collector on the reserved foil, then filling the current collector into an aluminum plastic film, sealing 2 polar lug edges and 1 side edge, and leaving one side edge unsealed for injecting liquid.
f. Weighing the mass of the cell before injecting liquid to obtain M0
(2) Injecting excessive electrolyte into the battery core which is not injected with the electrolyte; the mass of excess electrolyte is recorded as M1,M1Mass of electrolyte in 2 times pore volume, i.e. M1=2×V1×ρ1Where V1 is the pore volume, ρ1The pore volume can be calculated by the porosity of the pole piece and the diaphragm as the density of the electrolyte;
(3) according to actual process conditions, disassembling the battery cell after formation, pouring out redundant electrolyte, weighing the mass of the core package, and recording as M2Weighing the mass of the disassembled parts except the core bag, and recording as M3
(4) Calculating the net liquid amount (initial liquid amount) C ═ M2+M3-M0
(5) Performing gradient test, taking 3 gradient injection amounts upwards and downwards according to the value of the net liquid amount C, and respectively recording as C-3、C-2、C-1、C、C1、C2、C3Wherein the amount of change in each gradient is 1.8% of the net liquid amount;
(6) designing 7-gradient injection amount tests, and respectively injecting liquid into the cells without injecting liquid, wherein the mark is C-3、C-2、C-1、C、C1、C2、C3Disassembling the battery cell after formation, and recording the free liquid amount of the battery cell (see table 2);
TABLE 2
Experiment number Injection amount/g Amount of free liquid/g
C-3 141.9 2.61
C-2 144.6 2.64
C-1 147.3 2.65
C 150 2.67
C1 152.7 3
C2 155.4 4.54
C3 141.9 2.61
(7) And drawing a scatter diagram by taking the liquid injection amount as a horizontal coordinate and the free liquid amount as a vertical coordinate, determining an inflection point where the free liquid amount stably rises after connecting the lines, wherein the liquid injection amount corresponding to the inflection point is the optimal liquid injection amount.
As shown in fig. 2, the 5 th point is an inflection point, and the corresponding optimum injection amount is 152.7g, indicating that the electrolyte amount of the core pack has reached the saturation state under the current process conditions and design conditions.
As shown in FIG. 3, the cyclic data at different injection amounts were compared (test conditions: 2.75 to 4.3V, 1C/1C,25 ℃ C.), and C was observed1The cycle level of the shot size (152.7g) of (1) was optimum.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (8)

1. A method for determining the initial injection amount of a lithium ion battery is characterized in that: the method comprises the following steps: (1) weighing the quality of the battery cell without liquid injection to obtain M0(ii) a (2) Injecting excessive electrolyte into the battery core which is not injected with the electrolyte; (3) disassembling the battery core after formation, pouring out redundant electrolyte, weighing the mass of the core package, and recording the mass as M2Weighing the mass of the disassembled parts except the core bag, and recording as M3(ii) a (4) Calculating the amount of purified liquid C ═ M2+M3-M0And the net liquid amount is the initial liquid injection amount.
2. The method for determining the initial charge amount of the lithium ion battery according to claim 1, wherein: the mass of the excess electrolyte in the step (2) is recorded as M1,M1=2×V1×ρ1Where V1 is the pore volume, ρ1Is the electrolyte density.
3. The method for determining the initial charge amount of the lithium ion battery according to claim 2, wherein: the pore volume is obtained by calculating the porosity of the pole piece and the diaphragm.
4. A method for determining the liquid injection amount of a lithium ion battery is characterized by comprising the following steps: the method comprises the following steps: (1) weighing the quality of the battery cell without liquid injection to obtain M0(ii) a (2) Injecting excessive electrolyte into the battery core which is not injected with the electrolyte; (3) disassembling the battery core after formation, pouring out redundant electrolyte, weighing the mass of the core package, and recording the mass as M2Weighing the mass of the disassembled parts except the core bag, and recording as M3(ii) a (4) Calculating the amount of purified liquid C ═ M2+M3-M0(ii) a (5) Taking the liquid injection quantities of a plurality of gradients upwards and downwards according to the value of the net liquid quantity C, and respectively recording the liquid injection quantities as C-n……C-2、C-1、C、C1、C2……Cn(ii) a (6) Respectively injecting the obtained injection quantities of the gradients into a plurality of battery cores which are not injected with liquid, disassembling the battery cores after formation, and recording the free liquid quantity of the battery cores as B-n……B-2、B-1、B、B1、B2……Bn(ii) a (7) And drawing a scatter diagram by taking the liquid injection amount as a horizontal coordinate and the free liquid amount as a vertical coordinate, determining an inflection point of the stable rising of the free liquid amount after connecting the lines, wherein the liquid injection amount corresponding to the inflection point is the optimal liquid injection amount.
5. The method for determining the injection amount of the lithium ion battery according to claim 4, wherein: the variation of each gradient in the step (5) is 0.5-4% of the net liquid amount.
6. The method for determining the injection amount of the lithium ion battery according to claim 5, wherein: the variation of each gradient in the step (5) is 1.8% of the net liquid amount.
7. The method for determining the electrolyte injection amount of the lithium ion battery according to any one of claims 4 to 6, wherein: in the step (5), 3 gradients of liquid injection amounts are respectively taken upwards and downwards according to the value of the net liquid amount C and are recorded as C-3、C-2、C-1、C、C1、C2、C3
8. Use of the method for determining an amount of lithium ion battery charge according to claim 4, wherein: the method is applied to the soft package battery.
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CN115939694A (en) * 2022-08-17 2023-04-07 宁德时代新能源科技股份有限公司 Method for determining liquid injection amount of single battery
CN116151051A (en) * 2023-04-24 2023-05-23 四川新能源汽车创新中心有限公司 Method for determining lithium ion battery liquid injection amount
CN116151051B (en) * 2023-04-24 2023-08-15 四川新能源汽车创新中心有限公司 Method for determining lithium ion battery liquid injection amount
CN116666921A (en) * 2023-07-31 2023-08-29 宁德时代新能源科技股份有限公司 Liquid injection amount control method, device, equipment, medium, product and liquid injection system
CN116666921B (en) * 2023-07-31 2024-01-26 宁德时代新能源科技股份有限公司 A method for controlling the injection amount a device(s) Equipment, medium and liquid injection system

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