CN110676514B - Lithium ion battery monomer and formation method thereof - Google Patents
Lithium ion battery monomer and formation method thereof Download PDFInfo
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- CN110676514B CN110676514B CN201810711661.3A CN201810711661A CN110676514B CN 110676514 B CN110676514 B CN 110676514B CN 201810711661 A CN201810711661 A CN 201810711661A CN 110676514 B CN110676514 B CN 110676514B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 69
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 59
- 239000000178 monomer Substances 0.000 title claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 239000005022 packaging material Substances 0.000 claims abstract description 6
- 238000007600 charging Methods 0.000 claims description 60
- 239000002194 amorphous carbon material Substances 0.000 claims description 15
- 238000010277 constant-current charging Methods 0.000 claims description 11
- 239000006183 anode active material Substances 0.000 claims description 9
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- 239000006182 cathode active material Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 4
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- 230000020169 heat generation Effects 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 description 17
- 210000004027 cell Anatomy 0.000 description 16
- 238000011056 performance test Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229910003481 amorphous carbon Inorganic materials 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
-
- 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)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium batteries, and discloses a lithium ion battery monomer and a formation method thereof, wherein the lithium ion battery monomer comprises an anode, a cathode, a diaphragm, electrolyte and a packaging material, and the ratio of the anode capacity A to the cathode capacity B is 0.7-1. The lithium ion battery monomer has high energy density, high power density, low battery internal resistance, excellent quick charge performance and long cycle life, and is suitable for long-term use under the high-rate working condition; the highest cut-off capacity is cut off according to the anode capacity when the battery is formed by adopting the formation method, so that the safety of the battery formation process can be effectively improved; the lithium ion battery formed by the formation method has small internal resistance, the capacity is kept above 80% for 500 times of 5C charge-discharge circulation, and the surface temperature of the battery is low after 5C quick charge is finished, so that the heat generation in the quick charge process can be effectively reduced.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a lithium ion battery monomer and a formation method thereof.
Background
With the rapid development of new energy automobiles, the market has increasingly strong demand for the rapid charging performance of lithium ion batteries in recent years.
When the traditional lithium ion battery is charged under a lower multiplying power, lithium ions in the cathode material can be fully extracted and are embedded into the anode material structure. In the design of the battery, in order to prevent lithium dendrite precipitation on the surface of the anode during charging, the balance ratio of the anode capacity to the cathode capacity is more than 1. Lithium ion batteries using amorphous carbon or amorphous carbon containing materials as the anode are suitable for charging at high rates where polarization of the battery is unavoidable and thus lithium ions in the cathode material are not completely extracted and intercalated into the anode material structure. When a fast-charging lithium ion battery using amorphous carbon or a material containing amorphous carbon as an anode is designed according to the traditional battery, the balance ratio of the anode capacity to the cathode capacity is more than 1, which causes the disadvantages of increased electrode thickness, increased battery temperature, weakened fast-charging effect and the like.
The formation process of the lithium ion battery, also called a pre-charging process or a first charging process, refers to charging the battery in an uncharged state to make it a charged primary battery. Formation is an essential process in the production process of the lithium battery, and plays a crucial role in the performance of the lithium battery. Particularly for soft package lithium batteries, the formation not only has the functions of activating battery materials, improving lithium battery interfaces, self-discharging, circulating and the like, but also has the functions of enhancing the hardness of a battery core, shaping and the like. The traditional hot-pressing formation process has the problems of softening, lithium precipitation and the like.
CN102916224A discloses a formation method of a lithium ion battery, in which an anode active material used in the lithium ion battery includes an amorphous carbon material, the formation method at least includes two steps of charging and standing, and is characterized in that: the battery balance ratio of the lithium ion battery is (1.04-1): 1, the calculation formula of the cell balance ratio is (A)c×Aw)/(Cc×Cw×Cf×Af) Wherein A iscIs the first charge gram capacity of the anode active material, and the unit is mAh/g, AwMass of anode active material in g, CcThe first discharge gram capacity under the voltage is designed for the cathode active material, and the unit is mAh/g, CwIs the mass of the cathode active material, in g, CfFirst charge-discharge efficiency of the cathode active material, AfThe first charge-discharge efficiency of the anode active material; the anode potential is 0 at the end of the first charging formation03-0V.
When CN102916224A is formed for the first time, the anode potential is controlled to be 0.03-0V, some irreversible active points of the amorphous carbon material can be fully consumed, a complete SEI film is formed on the surface of the anode, and the high-temperature storage performance of the battery is improved. However, when the battery is designed, the balance ratio of the anode capacity to the cathode capacity is greater than 1, so that the battery is more suitable for charging at a lower rate, and when the battery is used for high-rate quick charging, the battery has the disadvantages of increased electrode thickness, increased internal resistance, weakened quick charging effect and the like.
Therefore, in order to overcome the defects of increased electrode thickness, increased internal resistance and reduced quick charge effect caused by the design of the traditional high-power lithium ion battery, research and development of a lithium ion battery and a formation method suitable for high-rate quick charge are necessary.
Disclosure of Invention
The invention aims to overcome the defects of increased electrode thickness, increased internal resistance and weakened quick charge effect caused by the design of the traditional high-power lithium ion battery, and provides a lithium ion battery monomer and a formation method thereof, wherein the ratio of the anode capacity A to the cathode capacity B of the lithium ion battery monomer is 0.7-1, and the lithium ion battery monomer has excellent quick charge performance and long cycle life; the highest cut-off capacity is cut off according to the anode capacity when the battery is formed by adopting the formation method, so that the safety of the battery formation process can be effectively improved; the lithium ion battery prepared by the formation method has small internal resistance, the 5C charging capacity retention rate is more than 75%, the capacity is kept more than 80% in 500 times of 5C charging and discharging cycles, the surface temperature of the battery is low after 5C quick charging is finished, and the heat generation in the quick charging process can be effectively reduced.
In order to achieve the above object, a first aspect of the present invention provides a lithium ion battery cell including an anode, a cathode, a separator, an electrolyte, and an encapsulant, wherein a ratio of an anode capacity a to a cathode capacity B is 0.7 to 1.
The second aspect of the present invention provides a method for forming a lithium ion battery cell, wherein the method at least comprises: and stopping charging the lithium ion battery monomer.
By the technical scheme, the balance ratio of the anode capacity to the cathode capacity of the single lithium ion battery is less than or equal to 1, so that the thickness of a negative pole piece is reduced, and the quick charge performance is improved; the internal resistance of the battery is reduced, the heating in the quick charging process is reduced, and the energy efficiency of the battery is improved; lithium consumed in the long-term quick charge cycle process of the battery can be supplemented, and the service life of the battery is prolonged; the usage amount of the cathode material is reduced, the weight of the battery is reduced, and meanwhile, the cost is relatively reduced. In addition, the highest cut-off capacity is cut off according to the anode capacity when the battery is formed by adopting the formation method, so that the safety of the battery formation process can be effectively improved; the lithium ion battery formed by the formation method has small internal resistance, the capacity is kept above 80% for 500 times of 5C charge-discharge circulation, and the surface temperature of the battery is low after 5C quick charge is finished, so that the heat generation in the quick charge process can be effectively reduced.
Drawings
FIG. 1 is a diagram of the surface state of an electrode after graphite anode maximum power (5C) charging;
FIG. 2 is a diagram of the electrode surface state after amorphous carbon anode maximum power (5C) charging;
FIG. 3 is a graph comparing the charge-discharge cycle life at large anode rate (5C) for lithium ion batteries S1-S3 prepared in examples 1-3 and lithium ion battery D1 prepared in comparative example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, one or more new ranges of values may be obtained from combinations of values between the endpoints of each range, the endpoints of each range and the individual values, and the individual values of the points, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a lithium ion battery monomer, which comprises an anode, a cathode, a diaphragm, electrolyte and a packaging material, wherein the ratio of the anode capacity A to the cathode capacity B is 0.7-1.
According to the invention, the ratio of the anode capacity a to the cathode capacity B is preferably between 0.85 and 1; in the invention, the ratio of the anode capacity A to the cathode capacity B is limited to be in the range, so that the thickness of the negative pole piece can be reduced, and the quick charge performance can be improved; the internal resistance of the battery can be reduced, the heating in the quick charging process is reduced, and the energy efficiency of the battery is improved; the lithium consumed in the long-term quick charge cycle process of the battery can be supplemented, and the service life of the battery is prolonged; and the use amount of the negative electrode material is reduced, the weight of the battery is reduced, and meanwhile, the cost is relatively reduced.
Preferably, the anode capacity a is a total anode active material capacity, and the cathode capacity B is a total cathode active material capacity.
According to the invention, the anode comprises an amorphous carbon material; preferably, the amorphous carbon material accounts for 5-99%, preferably 50-99% of the total mass of the anode active material; preferably, the amorphous carbon material includes at least one of soft carbon and hard carbon, and preferably, the amorphous carbon material includes soft carbon.
According to the invention, the cathode can be one or more of lithium cobaltate, lithium manganate, lithium nickel cobalt aluminate and lithium iron phosphate.
According to the present invention, the electrolyte may include an organic solvent, an additive, and a lithium salt.
Wherein, the organic solvent may be one or more of propylene carbonate pc (propylene carbonate), ethylene carbonate ec (ethylene carbonate) and dimethyl carbonate dec (dimethyl carbonate).
Wherein, the additive preferably comprises one or more of vinylene carbonate VC (vinylene carbonate), propylene sulfite PS (propylene sulfite) and fluoroethylene carbonate FEC (fluoroethylene carbonate); in the present invention, the additive is used in an amount of 0.5 to 5 wt% based on the total weight of the electrolyte.
Among them, the lithium salt may be preferably one or more of lithium hexafluorophosphate, lithium tetrafluoroborate and lithium hexafluoroarsenate, and the concentration of the lithium salt may be 1.2 to 2M, preferably 1.2 to 1.4M.
According to the invention, the diaphragm can be one or more of a PP (Polypropylene) film, a PE (Polyethylene) film and a PP/PE/PP composite film, the thickness of the diaphragm can be 16-26 μm in a preferable case, and the diaphragm is a PP/PE/PP composite film with the thickness of 20-25 μm in a more preferable case; most preferably, the diaphragm is a PP/PE/PP composite film with the thickness of 25 um; in the present invention, PP/PE/PP denotes a composite film in which a first PP film, a PE film, and a second PP film are compounded, wherein the first PP film and the second PP film may be the same PP film.
The packaging material can be one or more of an aluminum-plastic film packaging material, an aluminum shell and a steel shell, and is preferably an aluminum-plastic film packaging material.
The second aspect of the present invention provides a method for forming a lithium ion battery cell, wherein the method at least comprises: and stopping charging the lithium ion battery monomer.
According to the present invention, the charging includes a first constant current charging and a second constant current charging being cut off;
according to the present invention, the conditions of the first constant current charging include: the charging current is 0.01-1C, preferably 0.01-0.05C; the time is 100-1h, preferably 50-10 h.
According to the present invention, the conditions of the second constant current charging include: the charging current is 0.01-2C, preferably 0.1-2C, more preferably 0.1-1C; and stopping charging when the capacity of the lithium ion battery reaches the anode capacity A.
According to the invention, the formation method is adopted to cut off according to the anode capacity A during the formation of the battery, and the safety of the battery formation process can be effectively improved.
According to the invention, the internal resistance of the lithium ion battery after the formation method is small; the capacity is kept above 80% for 500 times in a 5C charge-discharge cycle, and the surface temperature of the battery is low after 5C quick charge is finished, so that the heat generation in the quick charge process can be effectively reduced.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the performance parameters were determined as follows:
(1) battery performance test (internal resistance test): testing the internal resistance of the battery by using an alternating current impedance instrument for the lithium battery after formation, wherein the alternating current impedance instrument is purchased from Tonghui and has the model number of TH 9310B;
(2)5C quick charge capacity retention rate and 5C end of charge battery surface temperature test: discharging the lithium battery after the formation is finished to cut-off voltage of 2.5V at constant current of 1C, then charging to cut-off voltage of 4.2V at constant current of 5C, and simultaneously recording the temperature of the central point of the surface of the battery; and 5 times of cycle test is carried out according to the program to obtain 5C charging average capacity, and the average temperature of the surface center point is tested when charging is finished.
(3)5C, charge-discharge cycle test: and discharging the lithium battery after the formation is finished to the cut-off voltage of 2.5V by using 5C constant current, then charging the lithium battery to the cut-off voltage of 4.2V by using 5C constant current, performing 500-time cycle test according to the program, and recording the charge-discharge capacity of each cycle.
Example 1
This example is for the purpose of illustrating a lithium ion battery cell and a formation method according to the present invention.
(1) Adopting a fast-charging type 1Ah flexible package lithium ion battery, and designing the battery according to the ratio of the anode capacity A to the cathode capacity B of 0.9;
the anode material is an amorphous carbon material, and the amorphous carbon material accounts for 95% of the total mass of the anode active substance;
the cathode material is 333 type nickel cobalt lithium manganate, and the cathode material accounts for 94% of the total mass of the anode active substance;
wherein, the diaphragm is a three-layer PP/PE/PP composite film with the thickness of 25 mu m;
wherein the concentration of the electrolyte is 1.3M (wherein, 2% of FEC additive);
wherein, the battery adopts plastic-aluminum membrane encapsulation.
(2) And (3) forming the manufactured battery into:
the first step is as follows: charging at 0.02C for 20 hours;
the second step is that: and (4) charging at a constant current of 0.1C, and stopping charging when the charging capacity is equal to the designed anode capacity of 4.2V.
The lithium battery after formation was designated as S1, and the results of the performance test were shown in table 1.
In addition, fig. 2 is a diagram of the electrode surface state after amorphous carbon anode maximum magnification (5C) charging;
as can be seen from fig. 2: the amorphous carbon material is different from graphite in structure, the amorphous carbon material is large in interlayer spacing, low in order degree, short in lithium ion transmission path, multiple in direction and high in lithium ion transport speed, so that the amorphous carbon material is used as an anode battery to be charged under a high multiplying power (5C), the phenomenon of lithium precipitation of the anode caused by high-current charging can be effectively avoided, and the surface of the amorphous carbon anode is free of lithium precipitation after the amorphous carbon anode is charged at the high multiplying power (5C).
Therefore, the amorphous carbon material is very suitable for being applied to the anode of the lithium ion battery with higher requirements on quick charge.
Example 2
This example is for the purpose of illustrating a lithium ion battery cell and a formation method according to the present invention.
A lithium ion battery was prepared according to the same formation method as in example 1, except that: the ratio of the anode capacity A to the cathode capacity B of the provided lithium ion battery cell is 0.7.
The lithium battery after formation was designated as S2, and the results of the performance test were shown in table 1.
Example 3
This example is to describe a lithium ion battery cell, a chemical conversion method, and a lithium ion battery according to the present invention.
A lithium ion battery was prepared according to the same formation method as in example 1, except that: the ratio of the anode capacity A to the cathode capacity B of the provided lithium ion battery cell is 1.
The lithium battery after formation was designated as S3, and the results of the performance test were shown in table 1.
Example 4
This example is for the purpose of illustrating a lithium ion battery cell and a formation method according to the present invention.
A lithium ion battery was prepared according to the same formation method as in example 1, except that: the ratio of the anode capacity A to the cathode capacity B of the provided lithium ion battery cell is 0.8.
The lithium battery after formation was designated as S4, and the results of the performance test were shown in table 1.
Example 5
This example is for the purpose of illustrating a lithium ion battery cell and a formation method according to the present invention.
A lithium ion battery was prepared according to the same formation method as in example 1, except that:
and (3) forming the manufactured battery into:
the first step is as follows: charging at 0.01C for 50 hours;
the second step is that: and (4) charging at a constant current of 0.1C, and stopping charging when the charging capacity is equal to the anode capacity.
The lithium battery after formation was designated as S5, and the results of the performance test were shown in table 1.
Example 6
This example is for the purpose of illustrating a lithium ion battery cell and a formation method according to the present invention.
A lithium ion battery was prepared according to the same formation method as in example 1, except that:
and (3) forming the manufactured battery into:
the first step is as follows: charging at 0.01C for 50 hours;
the second step is that: and 2C constant current charging, and stopping charging when the charging capacity is equal to the 4.2V anode capacity.
The lithium battery after formation was designated as S6, and the results of the performance test were shown in table 1.
Example 7
This example is for the purpose of illustrating a lithium ion battery cell and a formation method according to the present invention.
A lithium ion battery was prepared according to the same formation method as in example 1, except that: the amorphous carbon is hard carbon.
The lithium battery after formation was designated as S7, and the results of the performance test were shown in table 1.
Comparative example 1
A lithium ion battery was prepared according to the same formation method as in example 1, except that: the ratio of the anode capacity A to the cathode capacity B of the provided lithium ion battery cell is 1.1.
The lithium battery after formation is recorded as D1, and the performance test is carried out on the lithium battery, and the results are shown in Table 1.
Comparative example 2
A lithium ion battery was prepared according to the same formation method as in example 1, except that: the anode of the provided lithium ion battery monomer adopts graphite.
The lithium battery after formation is recorded as D2, and the performance test is carried out on the lithium battery, and the results are shown in Table 1.
In addition, fig. 1 is a state diagram of the electrode surface after graphite anode maximum magnification (5C) charging;
as can be seen from fig. 1: because graphite is used as an anode, the charging speed of the lithium ion battery is limited due to small interlayer spacing, long diffusion path and low lithium ion transport speed, the battery taking graphite as the anode is generally charged at a low multiplying power (less than 2C), once the charging speed is increased, the anode faces the potential safety hazard of surface lithium precipitation, the surface lithium precipitation is carried out after the graphite anode is charged at a high multiplying power (5C), and the capacity is rapidly reduced.
Comparative example 3
A lithium ion battery was prepared according to the same formation method as in example 1, except that:
and (3) forming the manufactured battery into:
the first step is as follows: charging at 0.01C for 50 hours;
the second step is that: and (4) charging at a constant current of 0.1C, and stopping charging when the charging capacity is equal to the cathode capacity.
The lithium battery after formation was recorded as D3, and the performance test was performed thereon, and the results are shown in table 1.
Comparative example 4
A lithium ion battery was prepared according to the same formation method as in example 1, except that: the ratio of the anode capacity A to the cathode capacity B of the provided lithium ion battery cell is 0.6.
The lithium battery after formation is recorded as D4, and the performance test is carried out on the lithium battery, and the results are shown in Table 1.
TABLE 1
| Numbering | Internal resistance (m omega) | 5C fast charge capacity retention | Surface temperature (. degree. C.) of 5C end-of-charge battery |
| Example 1 | 10.37 | 77％ | 35.1 |
| Example 2 | 9.65 | 80％ | 34.3 |
| Example 3 | 10.58 | 75％ | 35.6 |
| Example 4 | 10.12 | 77％ | 34.8 |
| Example 5 | 10.29 | 76％ | 35.3 |
| Example 6 | 10.31 | 76％ | 35.6 |
| Example 7 | 10.15 | 80％ | 34.1 |
| Comparative example 1 | 11.27 | 71％ | 37.3 |
| Comparative example 2 | 12.51 | 65％ | 38.2 |
| Comparative example 3 | 10.61 | 74％ | 39.1 |
| Comparative example 4 | 10.69 | 51％ | 35.7 |
From the results in table 1, it can be seen that the charge capacity of the lithium ion battery 5C prepared in examples S1-S7 by the method of the present invention is maintained above 75%, indicating that the method of the present invention can effectively improve the quick charge capacity of the battery; the internal resistance of the lithium ion battery from S1 to S7 is 9.65 to 10.37, which shows that the internal resistance of the battery can be reduced by the formation method of the invention; and the surface temperature of the S1-S7 lithium ion battery is 34.1-35.6 ℃, which shows that the formation method can effectively reduce the heat generation in the quick charge process.
In addition, fig. 3 is a graph comparing the charge-discharge cycle life at a large rate (5C) of the lithium ion batteries S1-S3 prepared in examples 1-3 and the lithium ion battery D1 prepared in comparative example 1, as can be seen in fig. 3: the battery prepared by the method can effectively prolong the cycle life of the battery, and the capacity retention rate is more than 80% after the battery is subjected to high-rate (5C) charge-discharge cycle for 500 times.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (9)
1. A method for forming a lithium ion battery cell is characterized by at least comprising the following steps: stopping charging and charging of the lithium ion battery monomer, wherein the charging comprises stopping of first constant current charging and second constant current charging; wherein the first constant current charging condition includes: the charging current is 0.01-1C, and the time is 100-1 h; the second constant current charging condition includes: the charging current is 0.01-2C; stopping charging when the capacity of the lithium ion battery reaches the anode capacity A;
the lithium ion battery monomer comprises an anode, a cathode, a diaphragm, electrolyte and a packaging material, and is characterized in that the ratio of the anode capacity A to the cathode capacity B is 0.7-1;
wherein the anode comprises an amorphous carbon material comprising soft and/or hard carbon;
wherein the electrolyte comprises an organic solvent, an additive and a lithium salt; and the additive is selected from one or more of vinylene carbonate, propylene sulfite and fluoroethylene carbonate; the organic solvent is propylene carbonate and/or dimethyl carbonate;
wherein the anode capacity A is the total capacity of the anode active material, and the cathode capacity B is the total capacity of the cathode active material.
2. The chemical conversion method according to claim 1, wherein the amorphous carbon material accounts for 5 to 99% of the total mass of the anode active material.
3. The formation method according to claim 2, wherein the amorphous carbon material accounts for 50-99% of the total mass of the anode active material.
4. The chemical conversion method according to claim 1, wherein the cathode is one or more of lithium cobaltate, lithium manganate, lithium nickel cobalt aluminate, and lithium iron phosphate.
5. The chemical conversion method according to claim 1, wherein the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate and lithium hexafluoroarsenate, and the concentration of the lithium salt is 1.2-2M.
6. The chemical synthesis method according to claim 1, wherein the separator is one or more of a PP film, a PE film and a PP/PE/PP composite film.
7. The chemical conversion method according to claim 6, wherein the thickness of the separator is 16-26 μm.
8. The chemical synthesis method according to claim 7, wherein the separator is a PP/PE/PP composite film with a thickness of 20-25 μm.
9. The formation method according to claim 1, wherein the condition of the first constant current charging includes: the charging current is 0.01-0.05C, and the time is 50-10 h; the second constant current charging condition includes: the charging current is 0.1-2C.
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