CN109216752B - Low-temperature lithium ion battery pack - Google Patents

Low-temperature lithium ion battery pack Download PDF

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CN109216752B
CN109216752B CN201710513902.9A CN201710513902A CN109216752B CN 109216752 B CN109216752 B CN 109216752B CN 201710513902 A CN201710513902 A CN 201710513902A CN 109216752 B CN109216752 B CN 109216752B
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battery
hot start
lithium ion
battery pack
batteries
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CN109216752A (en
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Qingdao Hengjinyuan Electronic 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/615—Heating or keeping warm
    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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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)
  • Secondary Cells (AREA)

Abstract

The invention provides a low-temperature lithium ion battery pack, wherein the battery pack comprises a plurality of battery strings in series connection, the battery strings are connected in parallel to form a battery pack, each battery string comprises a lithium ion battery and at least one hot start battery, each hot start battery comprises an anode, a cathode, a diaphragm and electrolyte, wherein the surface of the cathode is provided with an inorganic oxide layer, the thickness of the inorganic oxide layer is 20-40 micrometers, and the internal resistance of each hot start battery is higher than the internal resistance of other batteries in the battery string in which the hot start battery is arranged; when the battery pack is started at low temperature, at least one hot start battery in the battery string can generate more heat and is used as a heating source of the battery pack, so that the battery pack can quickly reach the normal working temperature, and the quick start of the battery pack and the heat preservation in a low-temperature environment are facilitated.

Description

Low-temperature lithium ion battery pack
Technical Field
The invention relates to the technical field of batteries, in particular to a low-temperature lithium ion battery pack.
Background
With the increasing prominence of the problems of environmental pollution, energy crisis, greenhouse effect and the like, people begin to pay more attention to rechargeable batteries. Batteries are the most important energy storage elements in electric vehicles and power storage stations, or mobile phones and notebook computers. The low-temperature charging of the battery is always a problem which is difficult to break through at present. At present, no unified solution is available for the problem of low-temperature charging of the battery. The general solution is to use external heating to heat the battery to normal temperature or above 10 ℃ for recharging, or to use heat insulating material and heat insulating material to ensure that the battery temperature does not drop too low. However, this method is limited by the environment and has a very limited improvement effect.
Disclosure of Invention
The invention provides a low-temperature lithium ion battery pack, wherein the battery pack comprises a plurality of battery strings in series connection, the battery strings are connected in parallel to form a battery pack, each battery string comprises a lithium ion battery and at least one hot start battery, each hot start battery comprises an anode, a cathode, a diaphragm and electrolyte, wherein the surface of the cathode is provided with an inorganic oxide layer, the thickness of the inorganic oxide layer is 20-40 micrometers, and the internal resistance of each hot start battery is higher than the internal resistance of other batteries in the battery string in which the hot start battery is arranged; when the battery pack is started at low temperature, at least one hot start battery in the battery string can generate more heat and is used as a heating source of the battery pack, so that the battery pack can quickly reach the normal working temperature, and the quick start of the battery pack and the heat preservation in a low-temperature environment are facilitated.
The specific scheme is as follows:
a low-temperature lithium ion battery pack comprises a plurality of battery strings in series connection, the battery strings are connected in parallel to form a battery pack, the battery strings comprise lithium ion batteries and at least one hot start battery, the hot start battery comprises an anode, a cathode, a diaphragm and electrolyte, wherein an inorganic oxide layer is arranged on the surface of the cathode, the thickness of the inorganic oxide layer is 20-40 micrometers, and the internal resistance of the hot start battery is higher than the internal resistances of other lithium ion batteries in the battery strings where the hot start battery is located.
Further, the inorganic oxide is selected from alumina, magnesia, zirconia and titania.
Further, the electrolyte of the hot-start battery also comprises a flame retardant.
Further, the thickness of the inorganic oxide layer is 24-26 microns.
Further, the capacity of the hot start battery in the battery string is higher than the capacity of other lithium ion batteries in the string.
Further, the method for preparing the battery pack comprises the following steps of forming the lithium ion batteries into groups, connecting the batteries in the same group with one or more hot start batteries in series to obtain a battery string, and connecting the battery string in parallel to obtain the battery pack.
The formation and matching method of the lithium ion battery comprises the following steps:
1) providing a group of lithium ion batteries to be formed, carrying out pulse charging on the batteries by using current of 0.02-0.05C, and stopping charging until the charging is cut off to voltage; wherein the pulse time is 0.1-10min, the interval time is 30-120s, and the charging cut-off voltage is 4.2-4.35V;
2) discharging the battery at a current of 0.05-0.2C until the discharge cutoff voltage is 2.7-2.8V;
3) repeating the step 1-2 for 0-3 times;
4) standing and aging for 1-5 days;
5) extracting electrolyte which is not immersed into the electrode in the battery shell, re-injecting new electrolyte, and sealing;
6) charging the battery with a current of 1-5C until the charging cut-off voltage is 4.2-4.35V, and discharging the battery with a current of 1-5C until the discharging cut-off voltage is 2.7-2.8V;
7) repeating the step 6 for 0-5 times, recording the capacity of the battery and the temperature of the battery, and matching the batteries with the capacity difference of 3% and the temperature difference of 5 ℃ into a group.
The invention has the following beneficial effects:
1. at least one hot start battery in the battery string can generate more heat, so that the battery string can be used as a heating source of the battery pack, and the battery pack can quickly reach the normal working temperature.
2. The addition of the flame retardant improves the high-temperature performance of the hot start battery and prolongs the service life of the hot start battery.
3. In the process of early formation, metal ions in the active material are inevitably partially dissolved into the electrolyte, and the process of forming the SEI film can also influence the composition of the electrolyte, and the influence can influence the performance of the battery, so that after the formation is finished, the electrolyte with changed components is extracted, and new electrolyte is injected again, and the storage life of the battery can be prolonged.
4. The concentration polarization on the surface of the electrode is eliminated through small-current pulse charging, so that a uniform and stable SEI film is formed, active substances of the electrode are fully activated through large-current charging and discharging cycles, the multiplying power performance of the battery is measured, the heat productivity of different batteries is amplified through increasing the current, and therefore batteries with similar capacity and same internal resistance are configured into a battery pack more accurately according to the capacity and the heat productivity of the batteries, and the uniformity of the battery pack is improved.
The battery pack which is long in service life, stable in performance and good in single battery performance consistency is constructed by the method.
Detailed Description
The present invention will be described in more detail below with reference to specific examples, but the scope of the present invention is not limited to these examples.
Example 1
A hot start battery is provided, which comprises a positive electrode with lithium cobaltate as a positive electrode active material, a negative electrode with artificial graphite as a negative electrode material, a porous alumina layer with the thickness of 20 microns is arranged on the surface of the negative electrode, a polyethylene diaphragm, and lithium hexafluorophosphate with the volume ratio of 1.2mol/L, wherein the volume ratio of the lithium hexafluorophosphate to the polyethylene diaphragm is 1: 1: 1 mixed non-aqueous solvent of dimethyl carbonate, diethyl carbonate, ethyl carbonate, and 10 vol% triethyl phosphate.
Secondly, configuring the battery pack
1) Providing a lithium ion battery to be formed, carrying out pulse charging on the battery with the current of 0.05C, and stopping charging until the voltage is cut off; wherein the pulse time is 10min, the interval time is 120s, and the charging cut-off voltage is 4.35V;
2) discharging the battery at a current of 0.2C to a discharge cutoff voltage, wherein the discharge cutoff voltage is 2.8V;
3) repeating the step 1-2 for 3 times;
4) standing and aging for 5 days;
5) the electrolyte which is not immersed in the electrode in the battery shell is extracted out, new electrolyte is injected again, and the sealing is carried out, wherein the new electrolyte comprises 1.2mol/L lithium hexafluorophosphate and the volume ratio is 1: 2: 1 of dimethyl carbonate, ethyl carbonate, a non-aqueous solvent consisting of ethyl methyl carbonate, and 5 volume percent of fluoroethylene carbonate;
6) charging the battery with a current of 5C until the charging cut-off voltage is 4.35V, discharging the battery with a current of 5C until the discharging cut-off voltage is 2.8V;
7) repeating the step 6 for 5 times, recording the capacity of the battery and the temperature of the battery, and matching the batteries with the capacity difference of 3% and the temperature difference of 5 ℃ into a group;
8) selecting 10 lithium ion batteries in the same group, and connecting the lithium ion batteries with a hot start battery in series to form a battery string, wherein the capacity of the hot start battery is 120% of the average capacity of other lithium ion batteries, and the internal resistance of the hot start battery is higher than that of other batteries;
9) and connecting the five groups of batteries in series and in parallel to obtain the battery pack.
Example 2
A hot start battery is provided, which comprises a positive electrode with lithium cobaltate as a positive electrode active material, a negative electrode with artificial graphite as a negative electrode material, a porous alumina layer with the thickness of 25 microns is arranged on the surface of the negative electrode, a polyethylene diaphragm, and lithium hexafluorophosphate with the volume ratio of 1.2mol/L, the volume ratio of lithium hexafluorophosphate is 1: 1: 1 mixed non-aqueous solvent of dimethyl carbonate, diethyl carbonate, ethyl carbonate, and 10 vol% triethyl phosphate.
Secondly, configuring the battery pack
1) Providing a lithium ion battery to be formed, carrying out pulse charging on the battery with the current of 0.02C, and stopping charging until the voltage is cut off; wherein the pulse time is 0.1min, the interval time is 30s, and the charging cut-off voltage is 4.2V;
2) discharging the battery at a current of 0.05C to a discharge cutoff voltage, wherein the discharge cutoff voltage is 2.7V;
3) repeating the step 1-2 for 0 times;
4) standing and aging for 1 day;
5) the electrolyte which is not immersed in the electrode in the battery shell is extracted out, new electrolyte is injected again, and the sealing is carried out, wherein the new electrolyte comprises 1.2mol/L lithium hexafluorophosphate and the volume ratio is 1: 2: 1 of dimethyl carbonate, ethyl carbonate, a non-aqueous solvent consisting of ethyl methyl carbonate, and 5 volume percent of fluoroethylene carbonate;
6) charging the battery with the current of 1C until the charging cut-off voltage is 4.2V, discharging the battery with the current of 1C until the discharging cut-off voltage is 2.7V;
7) repeating the step 6 for 1 time, recording the capacity of the battery and the temperature of the battery, and matching the batteries with the capacity difference of 1% and the temperature difference of 2 ℃ into a group;
8) selecting 10 lithium ion batteries in the same group, and connecting the lithium ion batteries with a hot start battery in series to form a battery string, wherein the capacity of the hot start battery is 125% of the average capacity of other lithium ion batteries, and the internal resistance of the hot start battery is higher than that of other batteries;
9) and connecting the five groups of batteries in series and in parallel to obtain the battery pack.
Example 3
A hot start battery is provided, which comprises a positive electrode with lithium cobaltate as a positive electrode active material, a negative electrode with artificial graphite as a negative electrode material, a porous alumina layer with the thickness of 30 microns is arranged on the surface of the negative electrode, a polyethylene diaphragm, and a lithium hexafluorophosphate layer containing 1.2mol/L of lithium hexafluorophosphate and the volume ratio of 1: 1: 1 mixed non-aqueous solvent of dimethyl carbonate, diethyl carbonate, ethyl carbonate, and 15 vol% triethyl phosphate.
Secondly, configuring the battery pack
1) Providing a lithium ion battery to be formed, carrying out pulse charging on the battery with the current of 0.03C, and stopping charging until the voltage is cut off; wherein the pulse time is 2min, the interval time is 40s, and the charging cut-off voltage is 4.3V;
2) discharging the battery at a current of 0.1C to a discharge cutoff voltage, wherein the discharge cutoff voltage is 2.75V;
3) repeating the step 1-2 for 2 times;
4) standing and aging for 3 days;
5) the electrolyte which is not immersed in the electrode in the battery shell is extracted out, new electrolyte is injected again, and the sealing is carried out, wherein the new electrolyte comprises 1.2mol/L lithium hexafluorophosphate and the volume ratio is 1: 2: 1 of dimethyl carbonate, ethyl carbonate, a non-aqueous solvent consisting of ethyl methyl carbonate, and 5 volume percent of fluoroethylene carbonate;
6) charging the battery by using the current of 3C until the charging cut-off voltage is 4.25V, and discharging the battery by using the current of 3C until the discharging cut-off voltage is 2.75V;
7) repeating the step 6 for 3 times, recording the capacity of the battery and the temperature of the battery, and matching the batteries with the capacity difference of 2% and the temperature difference of 3 ℃ into a group;
8) selecting 10 lithium ion batteries in the same group, and connecting the lithium ion batteries with a hot start battery in series to form a battery string, wherein the capacity of the hot start battery is 130 of the average capacity of other lithium ion batteries, and the internal resistance of the hot start battery is higher than that of other batteries;
9) and connecting the five groups of batteries in series and in parallel to obtain the battery pack.
Example 4
A hot start battery is provided, which comprises a positive electrode with lithium cobaltate as a positive electrode active material, a negative electrode with artificial graphite as a negative electrode material, a porous alumina layer with the thickness of 35 microns is arranged on the surface of the negative electrode, a polyethylene diaphragm, and lithium hexafluorophosphate with the volume ratio of 1.2mol/L, wherein the volume ratio of the lithium hexafluorophosphate to the polyethylene diaphragm is 1: 1: 1 mixed non-aqueous solvent of dimethyl carbonate, diethyl carbonate, ethyl carbonate, and 15 vol% triethyl phosphate.
Secondly, configuring the battery pack
1) Providing a lithium ion battery to be formed, carrying out pulse charging on the battery with the current of 0.04C, and stopping charging until the charging is cut off to the voltage; wherein the pulse time is 8min, the interval time is 80s, and the charging cut-off voltage is 4.25V;
2) discharging the battery at a current of 0.15C to a discharge cutoff voltage, wherein the discharge cutoff voltage is 2.75V;
3) repeating the step 1-2 for 2 times;
4) standing and aging for 2 days;
5) the electrolyte which is not immersed in the electrode in the battery shell is extracted out, new electrolyte is injected again, and the sealing is carried out, wherein the new electrolyte comprises 1.2mol/L lithium hexafluorophosphate and the volume ratio is 1: 2: 1 of dimethyl carbonate, ethyl carbonate, a non-aqueous solvent consisting of ethyl methyl carbonate, and 5 volume percent of fluoroethylene carbonate;
6) charging the battery by using the current of 4C until the charging cut-off voltage is reached, wherein the charging cut-off voltage is 4.25V, discharging the battery by using the current of 4C until the discharging cut-off voltage is reached, and wherein the discharging cut-off voltage is 2.75V;
7) repeating the step 6 for 4 times, recording the capacity of the battery and the temperature of the battery, and matching the batteries with the capacity difference of within 1% and the temperature difference of within 3 ℃ into a group;
8) selecting 10 lithium ion batteries in the same group, and connecting the lithium ion batteries with a hot start battery in series to form a battery string, wherein the capacity of the hot start battery is 140% of the average capacity of other lithium ion batteries, and the internal resistance of the hot start battery is higher than that of other batteries;
9) and connecting the five groups of batteries in series and in parallel to obtain the battery pack.
Example 5
A hot start battery is provided, which comprises a positive electrode with lithium cobaltate as a positive electrode active material, a negative electrode with artificial graphite as a negative electrode material, a porous alumina layer with the thickness of 40 microns is arranged on the surface of the negative electrode, a polyethylene diaphragm, and lithium hexafluorophosphate with the volume ratio of 1.2mol/L, wherein the volume ratio of the lithium hexafluorophosphate to the polyethylene diaphragm is 1: 1: 1 mixed non-aqueous solvent of dimethyl carbonate, diethyl carbonate, ethyl carbonate, and 15 vol% triethyl phosphate.
Secondly, configuring the battery pack
1) Providing a lithium ion battery to be formed, carrying out pulse charging on the battery with the current of 0.03C, and stopping charging until the voltage is cut off; wherein the pulse time is 5min, the interval time is 60s, and the charging cut-off voltage is 4.3V;
2) discharging the battery at a current of 0.1C to a discharge cutoff voltage, wherein the discharge cutoff voltage is 2.8V;
3) repeating the step 1-2 for 1 time;
4) standing and aging for 2 days;
5) the electrolyte which is not immersed in the electrode in the battery shell is extracted out, new electrolyte is injected again, and the sealing is carried out, wherein the new electrolyte comprises 1.2mol/L lithium hexafluorophosphate and the volume ratio is 1: 2: 1 of dimethyl carbonate, ethyl carbonate, a non-aqueous solvent consisting of ethyl methyl carbonate, and 5 volume percent of fluoroethylene carbonate;
6) charging the battery by using the current of 2C until the charging cut-off voltage is reached, wherein the charging cut-off voltage is 4.3V, discharging the battery by using the current of 2C until the discharging cut-off voltage is reached, and wherein the discharging cut-off voltage is 2.8V;
7) repeating the step 6 for 4 times, recording the capacity of the battery and the temperature of the battery, and matching the batteries with the capacity difference of within 1% and the temperature difference of within 2 ℃ into a group;
8) selecting 10 lithium ion batteries in the same group, and connecting the lithium ion batteries with a hot start battery in series to form a battery string, wherein the capacity of the hot start battery is 140% of the average capacity of other lithium ion batteries, and the internal resistance of the hot start battery is higher than that of other batteries;
9) and connecting the five groups of batteries in series and in parallel to obtain the battery pack.
Comparative example 1
1) Selecting a group of lithium ion batteries, carrying out charge-discharge circulation for three times, wherein the charge cut-off voltage is 4.2V, and the discharge cut-off voltage is 2.7V, and measuring the capacity of the lithium ion batteries;
2) preparing a group of lithium ion batteries with the capacity difference within 1%;
3) and selecting 11 lithium ion batteries to be connected in series to form a battery string, and connecting five groups of batteries in series and parallel to obtain the battery pack.
Test and results
The batteries of examples 1 to 5 and the battery of comparative example were started at-20 ℃ and-50 ℃ and the time from start-up to normal operation was measured; performing charge-discharge cycle 300 times at a current of 0.5C, and measuring the cycle capacity retention rate; the experimental data of examples 1 to 5 and comparative example 1 are shown in table 1, and the batteries of examples 1 to 5 have shorter start-up time and higher capacity retention rate.
TABLE 1
Figure BDA0001336205460000071
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention.

Claims (3)

1. A low-temperature lithium ion battery pack is characterized in that the battery pack comprises a plurality of battery strings in series connection, the battery strings are connected in parallel to form the battery pack, each battery string comprises a lithium ion battery and at least one hot start battery, each hot start battery comprises a positive electrode, a negative electrode, a diaphragm, electrolyte immersed into the electrodes and electrolyte not immersed into the electrodes, and new electrolyte is injected again after the electrolyte is extracted, wherein the surface of the negative electrode is provided with an inorganic oxide layer, and the internal resistance of each hot start battery is higher than the internal resistance of other lithium ion batteries in the battery string where the hot start battery is located;
the inorganic oxide is magnesium oxide;
wherein the electrolyte of the hot start battery also comprises a flame retardant;
the thickness of the inorganic oxide layer is 24-26 microns;
in the same battery string, the capacity of the hot start battery is more than 120% of the average capacity of other lithium ion batteries.
2. The battery pack of claim 1, wherein the capacity of a hot start cell in the string is higher than the capacity of other lithium ion cells in the string in which it is located.
3. A method of making a battery according to any of claims 1 or 2, comprising the steps of grouping lithium ion batteries, connecting the batteries of the same group in series with one or more hot start batteries to form a battery string, and connecting the battery strings in parallel to form the battery.
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CN1917270A (en) * 2006-09-01 2007-02-21 天津力神电池股份有限公司 Method for increasing safe performance of square lithium ion secondary battery
CN101055925A (en) * 2007-02-02 2007-10-17 东莞新能源电子科技有限公司 A secure lithium icon battery, improving method and making method of its anode slice
CN104916848A (en) * 2015-05-05 2015-09-16 哈尔滨天宝石墨科技发展有限公司 Method for improving battery low-temperature starting performance
CN105529508A (en) * 2014-06-30 2016-04-27 比亚迪股份有限公司 Battery heating system, battery device and electric vehicle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1917270A (en) * 2006-09-01 2007-02-21 天津力神电池股份有限公司 Method for increasing safe performance of square lithium ion secondary battery
CN101055925A (en) * 2007-02-02 2007-10-17 东莞新能源电子科技有限公司 A secure lithium icon battery, improving method and making method of its anode slice
CN105529508A (en) * 2014-06-30 2016-04-27 比亚迪股份有限公司 Battery heating system, battery device and electric vehicle
CN104916848A (en) * 2015-05-05 2015-09-16 哈尔滨天宝石墨科技发展有限公司 Method for improving battery low-temperature starting performance

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