CN107959071B - A kind of lithium ion battery and its chemical synthesizing method - Google Patents
A kind of lithium ion battery and its chemical synthesizing method Download PDFInfo
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- CN107959071B CN107959071B CN201711128167.6A CN201711128167A CN107959071B CN 107959071 B CN107959071 B CN 107959071B CN 201711128167 A CN201711128167 A CN 201711128167A CN 107959071 B CN107959071 B CN 107959071B
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000000126 substance Substances 0.000 title claims abstract description 40
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000007600 charging Methods 0.000 claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 28
- 239000011572 manganese Substances 0.000 claims abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 24
- 239000010405 anode material Substances 0.000 claims abstract description 12
- 239000006182 cathode active material Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 11
- 230000005611 electricity Effects 0.000 claims description 7
- 206010016766 flatulence Diseases 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 5
- 238000010280 constant potential charging Methods 0.000 description 14
- 238000011056 performance test Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 238000001994 activation Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 229910009549 Li1.5Mn0.75Ni0.25O2.5 Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229920006255 plastic film Polymers 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
A kind of chemical synthesizing method of lithium ion battery, the cathode active material of lithium ion battery contains lithium-rich manganese-based anode material, chemical synthesizing method includes at least charge and discharge cycles three times, the preceding charge cutoff voltage of charge and discharge cycles twice is lower than 4.4V, and discharge current is greater than charging current and second of charging current is greater than first time charging current；Last time charge-discharge cycle charge cutoff voltage is not less than 4.4V, and charging current is not less than second of charging current.The present invention uses the formation regime of step voltage charge and discharge, stable SEI Mo ﹑ can not only be formed in negative terminal surface during multiple low-voltage charge and discharge and be conducive to positive electrode surface form stable CEI film, inhibit electrolyte under high voltages with pole piece side reaction, reduce gas generation, to solve battery flatulence problem, meanwhile this method can also improve the structural stability and capacity performance of lithium-rich manganese-based anode material under high pressure, improve the cycle performance and energy density of the battery.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of lithium ion battery and its chemical synthesizing method.
Background technique
Lithium ion battery is widely used in laptop, mobile phone as a kind of novel high-energy green battery
It on equal portable electronic products, and is expanded to the fields such as large and medium-sized energy storage device and new energy electric motor vehicle, this is to lithium ion battery
More stringent requirements are proposed for energy density and safety etc..
Currently, power battery is mainly negative using ternary layered positive electrode or lithium iron phosphate positive material and graphite both at home and abroad
Pole, energy density≤180Wh/kg.But according to Japan in its " NEDO next generation's automotive battery technological development route
Figure 20 13 " in, proposition is improved to the year two thousand twenty energy-type cells module energy density to 250Wh/Kg (note: by single battery energy
Density is about 75~80% calculating of module, and single battery energy density should reach 310Wh/kg or more)；U.S. USABC is proposed
Power battery of electric motor car long-run development target be 200Wh/kg ((note: by single battery energy density be about module 75~
80% calculates, and single battery energy density should reach 250Wh/kg or more).It is also set up in the five-year plan of the 13rd, China
New-energy automobile emphasis researches and develops special (2016-2020), and propose wherein single battery energy density reach 300 (Wh)/
kg.However, being calculated according to the design of nickel system high specific energy batteries it is found that nickel system high capacity positive electrode system battery energy density is more difficult
Meet the needs of the year two thousand twenty high specific energy batteries, it is therefore desirable to have the electrode material of more height ratio capacity is applied to lithium ion battery neck
Domain.Wherein, novel lithium-rich manganese-based anode material is in charging voltage >=4.6V (vsLi/Li+) when have specific discharge capacity it is high (>=
250mAhg-1) advantage, therefore widely paid close attention to by domestic and international researcher and enterprise.
But the performance of lithium-rich manganese-based anode material high capacity needs 4.5-4.6V (vs Li/ during initial charge
Li+) voltage platform activate.The researchs such as Armstrong and Bruce discovery is lithium-rich manganese-based just in 4.5-4.6V voltage platform
Pole material carries out activation and generates gas with the presence of oxygen release and electrolyte and electrode surface side reaction, in addition, transition metal
Ion moves to lithium layer from transition metal layer, leads to material structure steady decrease.
As it can be seen that being with lithium-rich manganese-based active material if being directly applied to the chemical synthesizing method for being suitable for conventional lithium ion battery
(stop charging after low current (0.01-0.1C) constant-current charge to certain depth of charge, or on the lithium ion battery of cathode with ladder
The size of current of formula charges to certain depth of charge and stops charging, if charge cutoff voltage is lower (≤4.4V), then filling for the first time
Lithium-rich manganese-based lithium ion battery can not activate release high capacity in electric process, if charge cutoff voltage is higher (>=4.4V), Fu Li
High-pressure trend during activation at, there are serious flatulence problem, causing electrode structure to destroy for the first time for manganese base lithium ion battery, this is seriously
Hinder the commercialized application of lithium-rich manganese-based lithium ion battery.Therefore, the chemical synthesizing method for being suitble to lithium-rich manganese-based anode material is found
One of hot spot as this field.
CN 103647115A is proposed the lithium-rich manganese-based battery of institute under high voltages into after activation (blanking voltage > 4.4V)
Battery low-voltage carry out charge and discharge cycles, although battery by activation so that rich lithium manganese base solid solution material is released Gao Rong
It measures, capacity and cyclical stability with higher under lower charge cutoff voltage, but causes since initial activation voltage is higher
Battery serious flatulence in activation process for the first time, which consumes electrolyte and destroys electrode structure, to be stablized, the final long circulating for influencing battery
Stability.2013/0043843 A1 of US proposes the stable circulation that low-voltage mise-a-la-masse method stage by stage improves lithium-rich manganese-based battery
Property, but due to its formation voltage < 4.4V, so the capacity of the battery plays the lower need for being unable to satisfy high-specific energy battery
It asks.
Based on this, it is necessary to provide and a kind of be directed to the lithium ion battery that cathode includes lithium-rich manganese-based anode active material
On the one hand chemical synthesizing method can make positive active material obtain activation release high capacity, on the other hand be formed surely in positive electrode surface
Fixed CEI film inhibits the electrolyte evolution with oxygen in the further side reaction of pole piece and active material under high voltages, improves material
The structural stability of material, and then solve battery flatulence problem.
Summary of the invention
For this purpose, one of the objects of the present invention is to provide a kind of chemical synthesizing method of lithium ion battery, this method solve with
Rich lithium manganese base solid solution material be active material lithium ion battery flatulence the technical issues of and improve lithium-rich manganese-based lithium from
The cycle performance and high rate performance of sub- battery.Method of the invention improves cycle performance, good rate capability and security performance, and
It is a kind of chemical synthesizing method of not lithium-rich manganese-based lithium ion battery of flatulence.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of chemical synthesizing method of lithium ion battery, the cathode active material of the lithium ion battery contain lithium-rich manganese-based anode
Material, the chemical synthesizing method include at least charge and discharge cycles three times, which is characterized in that the charge cutoff of preceding charge and discharge cycles twice
Voltage is lower than 4.4V, and discharge current is greater than charging current and second of charging current is greater than first time charging current；For the last time
The charge cutoff voltage of charge and discharge cycles is not less than 4.4V, and charging current is not less than the charging electricity of second of charge and discharge cycles
Stream.
The present invention use lower voltage at combine Towards Higher Voltage at step voltage charge and discharge formation regime to containing richness
Lithium Mn-based material is that the lithium ion battery with high energy density of anode is melted into, during multiple low-voltage charge and discharge not only
Stable SEI Mo ﹑ capable of being formed in negative terminal surface and being conducive to positive electrode surface and form stable CEI film, electrolyte is inhibited to exist
With pole piece side reaction under high voltage, reduce gas generation, so that battery flatulence problem is solved, meanwhile, this method can also improve
Lithium-rich manganese-based anode material structural stability under high pressure and capacity play, improve the cycle performance and energy of the battery
Density.
Preferably, the discharge current of charge and discharge cycles is greater than charging current and is not more than 1.0C.
Preferably, the chemical synthesizing method the following steps are included:
Step 1, to lithium ion battery with electric current I0Constant-current charge 0-10h, when being 0, I0=I1, then with electric current I1It carries out permanent
Ductility limit pressure charging, blanking voltage V1；With electric current D1Constant-current discharge, until voltage is V1ˊ, and meet following condition:
0.005C≤I0≤ 0.1C, 0.005C≤I1≤ 0.2C, 4.1V≤V1< 4.4V, and
I1< D1≤ 1.0C, 2.0V≤V1ˊ < 2.8V；
Step 2, with electric current I2Carry out onstant current voltage limiting to charge, blanking voltage V2；With electric current D2Constant-current discharge, until voltage is V2
ˊ, and meet following condition:
I1< I2≤0.2C,V1≤V2< 4.4V, and
I2< D2≤ 1.0C, 2.0V≤V2ˊ < 2.8V；
Step 3 ... n-1, with electric current I3……In-1Carry out onstant current voltage limiting to charge, blanking voltage V3……Vn-1；With electricity
Flow D3……n-1Constant-current discharge, until voltage is V3ˊ……Vn-1ˊ, and meet following condition:
I2≤I3……In-1≤0.2C,V2≤V3……Vn-1≤Vn, and
I3……In-1< D3……Dn-1≤ 1.0C, 2.0V≤V3ˊ……Vn-1ˊ≤2.8V, n >=3；
Step n, with electric current InCarry out onstant current voltage limiting to charge, blanking voltage Vn；With electric current DnConstant-current discharge, until voltage is Vn
ˊ, and meet following condition:
I2≤In≤0.2C,4.4V≤Vn≤ 4.8V, and
In< Dn≤ 1.0C, 2.0V≤Vnˊ≤2.8V, n >=3.
Preferably, electric current I1,2Range be 0.01C-0.2C, blanking voltage V1,2Range be 4.20V-4.35V.
Preferably, electric current D1,2Range be 0.01C-0.5C, blanking voltage V ˊ1,2Range be 2.0-2.5V.
Preferably, electric current I3……InRange be 0.01C-0.2C, blanking voltage VnRange be 4.45V-4.8V.
Preferably, electric current D3……DnRange be 0.01C-0.5C, blanking voltage V ˊ3……VˊnRange be 2.0-
2.5V。
Preferably, it is characterized in that, the step of chemical conversion carried out in the environment of 0-60 DEG C.
An object of the present invention, which also resides in, provides a kind of lithium ion battery, including anode, cathode and be placed in anode with it is negative
The charge cutoff voltage of diaphragm between pole, the battery is greater than 4.3V and is less than or equal to 5.0V, uses of the present invention
The chemical synthesizing method of lithium ion battery.
The beneficial effects of the present invention are:
(1) present invention uses the chemical conversion side of step voltage charge and discharge to the lithium-rich manganese-based lithium ion battery for making positive electrode
Formula can not only form stable SEI film in negative terminal surface during multiple low-voltage charge and discharge, and be conducive to anode
Surface forms stable CEI film, inhibits the electrolyte ease with oxygen in anode pole piece side reaction and active material under high voltages
Out, reduce gas generation, to solve battery flatulence problem；
(2) chemical synthesizing method provided by the present invention, last time are melted into blanking voltage >=4.4, can make lithium-rich manganese-based
Material sufficiently activates, and high capacity is discharged, to improve the energy density of battery；
(3) present invention carries out lithium ion battery to charge to setting voltage, then carries out constant current to lithium ion battery again and puts
The mode of electricity can effectively slow down battery pole piece expansion accumulation, prevent pole piece cracking, corrugation；To improve material, electrode knot
Structure stability, and then improve the cyclical stability of battery；
(4) the used formation regime of the present invention is that discharge current is greater than charging current, and low charging current is conducive to positive and negative anodes
Surface forms stable SEI film, and discharge current is greater than charging current and is conducive to shorten the chemical conversion time；
(5) in addition, present invention process is simple, it is not necessary that the resources such as formation device are carried out with additional investment in research and development, cost is small,
It can be realized industrialized production, therefore have a good application prospect.
Detailed description of the invention
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing and table to the present invention
It is described in further detail, in which:
Fig. 1 is the photo figure of battery after 4 chemical synthesis technology of embodiment；
Fig. 2 is the photo figure of battery after 1 chemical synthesis technology of comparative example；
Fig. 3 is the mass energy density figure that battery is made in 1 chemical synthesis technology of embodiment.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The present embodiment cathode active material uses lithium-rich manganese-based anode material (Li1.5Mn0.75Ni0.25O2.5), anode active matter
Then naked battery core is put by matter using the naked battery core of high-energy type Soft Roll lamination that silicon-carbon is compound, diaphragm is prepared into 30Ah or so
It in aluminum plastic film through forming, is then packaged, dries and fluid injection.
Battery after fluid injection is melted into, 25 DEG C of temperature is melted into, it is as follows to be embodied in process:
(1) after with the multiplying power charging 5h of 0.01C, then with the multiplying power progress constant-current charge of 0.02C, until voltage is 4.2V,
Stand 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.03C, until voltage is 2.5V, stands 30min；
(2) constant-current charge is carried out with the multiplying power of 0.04C, until voltage is 4.2V, stands 30min；With the multiplying power of 0.5C into
Row constant-current discharge extremely, until voltage is 2.5V, stands 30min；
(3) constant-current charge is carried out with the multiplying power of 0.05C, until voltage is 4.6V, stands 30min；With the multiplying power of 0.5C into
Row constant-current discharge extremely, until voltage is 2.5V, stands 30min；
Secondary encapsulation is carried out to the lithium ion battery after chemical conversion, extracts lithium vacuum out, and carry out forming operation and obtain flexible package
Battery A1.
Capacity calibration and cycle performance test are being carried out to A1 battery, the specific test method is as follows:
Capacity calibration: by above-described lithium ion battery with the multiplying power constant current charge of 0.3C, until voltage value reaches
4.6V, then 4.6V carry out constant voltage charging, until current value is 0.03C, stand 30min；Then by lithium ion battery with
The multiplying power of 1.0C carries out constant-current discharge, stands 30min, obtains capacity Q1.
Cycle performance test: by above-described lithium ion battery with the multiplying power constant current charge of 0.5C, until voltage value
Reach 4.5V；4.5V carries out constant voltage charging again, until current value is 0.05C；Then by lithium ion battery with times of 1.0C
Rate carries out constant-current discharge.To lithium ion battery carry out 300 cycle charge-discharges, will calculate 300 times circulation after capacity with for the first time
The capacity ratio of circulation, i.e. capacity retention ratio.
Embodiment 2
The present embodiment cathode active material uses lithium-rich manganese-based anode material (Li1.5Mn0.75Ni0.25O2.5), anode active matter
Matter is prepared into the naked battery core of high-energy type Soft Roll lamination of 30Ah or so using silicon-carbon cathode, diaphragm, is then put into naked battery core
It in aluminum plastic film through forming, is then packaged, dries and fluid injection.
Battery after fluid injection is melted into, 25 DEG C of temperature is melted into, it is as follows to be embodied in process:
(1) after with the multiplying power charging 10h of 0.01C, then with the multiplying power progress constant-current charge of 0.03C, until voltage is 4.2V,
Stand 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.05C, until voltage is 2.2V, stands 30min；
(2) constant-current charge is carried out with the multiplying power of 0.05C, until voltage is 4.3V, stands 30min；With the multiplying power of 0.5C into
Row constant-current discharge extremely, until voltage is 2.3V, stands 30min；
(3) constant-current charge is carried out with the multiplying power of 0.1C, until voltage is 4.4V, stands 30min；It is carried out with the multiplying power of 0.5C
Constant-current discharge extremely, until voltage is 2.4V, stands 30min；
(4) constant-current charge is carried out with the multiplying power of 0.1C, until voltage is 4.7V, stands 30min；It is carried out with the multiplying power of 0.5C
Constant-current discharge extremely, until voltage is 2.5V, stands 30min；
Specific performance test is same as Example 1.
Embodiment 3
Flexible packing lithium ion battery A3 is prepared in the method for repeating embodiment 1, and chemical conversion temperature is 25 DEG C, but and embodiment
The chemical conversion process of the present embodiment is as follows unlike 1:
(1) after with the multiplying power charging 2h of 0.05C, then with the multiplying power progress constant-current charge of 0.05C, until voltage is 4.0V,
Stand 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.2C, until voltage is 2.0V, stands 30min；
(2) constant-current charge is carried out with the multiplying power of 0.1C, until voltage is 4.0V, stands 30min；It is carried out with the multiplying power of 0.5C
Constant-current discharge extremely, until voltage is 2.0V, stands 30min；
(3) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.3V, stands 30min；It is carried out with the multiplying power of 0.5C
Constant-current discharge extremely, until voltage is 2.0V, stands 30min；
(4) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.4V, stands 30min；It is carried out with the multiplying power of 0.5C
Constant-current discharge extremely, until voltage is 2.0V, stands 30min；
(5) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.45V, stands 30min；With the multiplying power of 0.5C into
Row constant-current discharge extremely, until voltage is 2.0V, stands 30min；
(6) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.45V, stands 30min；With the multiplying power of 0.5C into
Row constant-current discharge extremely, until voltage is 2.0V, stands 30min；
(7) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.6V, stands 30min；It is carried out with the multiplying power of 0.5C
Constant-current discharge extremely, until voltage is 2.0V, stands 30min；
(8) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.6V, stands 30min；It is carried out with the multiplying power of 1.0C
Constant-current discharge extremely, until voltage is 2.0V, stands 30min；
Specific performance test is same as Example 1.
Embodiment 4
Flexible packing lithium ion battery A4 is prepared in the method for repeating embodiment 1, and chemical conversion temperature is 25 DEG C, but and embodiment
The chemical conversion process of the present embodiment is as follows unlike 1:
(1) after with the multiplying power charging 1h of 0.05C, then with the multiplying power progress constant-current charge of 0.05C, until voltage is 4.1V,
4.1V carries out constant voltage charging again, until current value is 0.01C, stands 30min；Constant-current discharge is carried out with the multiplying power of 0.1C
Extremely, until voltage is 2.8V, 30min is stood；
(2) constant-current charge is carried out with the multiplying power of 0.075C, until voltage is 4.1V, then 4.1V carries out constant voltage charging,
Until current value is 0.02C, 30min is stood；Constant-current discharge is carried out extremely with the multiplying power of 0.2C, until voltage is 2.8V, is stood
30min；
(3) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.2V, then 4.2V carries out constant voltage charging, directly
It is 0.03C to current value, stands 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.3C, until voltage is 2.8V, is stood
30min；
(4) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.2V, then 4.2V carries out constant voltage charging, directly
It is 0.01C to current value, stands 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.5C, until voltage is 2.8V, is stood
30min；
(5) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.3V, then 4.3V carries out constant voltage charging, directly
It is 0.01C to current value, stands 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.5C, until voltage is 2.8V, is stood
30min；
(6) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.3V, then 4.3V carries out constant voltage charging, directly
It is 0.01C to current value, stands 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.5C, until voltage is 2.8V, is stood
30min；
(7) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.4V, then 4.4V carries out constant voltage charging, directly
It is 0.01C to current value, stands 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.5C, until voltage is 2.0V, is stood
30min；
(8) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.4V, then 4.4V carries out constant voltage charging, directly
It is 0.01C to current value, stands 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.5C, until voltage is 2.0V, is stood
30min；
(9) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.6V, then 4.6V carries out constant voltage charging, directly
It is 0.01C to current value, stands 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.5C, until voltage is 2.5V, is stood
30min；
(10) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.6V, then 4.6V carries out constant voltage charging, directly
It is 0.01C to current value, stands 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.5C, until voltage is 2.5V, is stood
30min；
(11) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.7V, then 4.7V carries out constant voltage charging, directly
It is 0.01C to current value, stands 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.5C, until voltage is 2.5V, is stood
30min；
(12) constant-current charge is carried out with the multiplying power of 0.2C, until voltage is 4.7V, then 4.7V carries out constant voltage charging, directly
It is 0.01C to current value, stands 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.5C, until voltage is 2.5V, is stood
30min；
Specific performance test is same as Example 1.
Embodiment 5
The present embodiment cathode active material uses 70wt% lithium-rich manganese-based anode material (Li1.5Mn0.75Ni0.25O2.5) and
30wt% high voltage LiMn2O4 (LiNi0.5Mn1.5O4), anode active material is prepared into 30Ah or so using silicon-carbon cathode, diaphragm
The naked battery core of high-energy type Soft Roll lamination, then naked battery core is put into the aluminum plastic film of forming, is then packaged, does
Dry and fluid injection.
It is embodied in mode such as embodiment 1；
Performance test such as embodiment 1；Gas situation such as Fig. 1 institute, the nothing in airbag after this method is melted into are produced after the Battery formation
Gas generates；The energy density of the battery about 300Wh/kg, as shown in Figure 3.
Embodiment 6
The present embodiment cathode active material uses 50wt% lithium-rich manganese-based anode material (Li1.5Mn0.75Ni0.25O2.5) and
50wt% high voltage cobalt acid lithium (LiCoO2), anode active material is prepared into the high energy of 30Ah or so using natural graphite, diaphragm
Naked battery core, is then put into the aluminum plastic film of forming, is then packaged, dries and infuses by the naked battery core of amount type Soft Roll lamination
Liquid；
It is embodied in mode such as embodiment 3；
Performance test such as embodiment 1.
Comparative example 1
Flexible packing lithium ion battery B1, but this implementation unlike the first embodiment is prepared in the method for repeating embodiment 1
Example uses traditional chemical conversion process, is melted into 25 DEG C of temperature, it is as follows to be embodied in process:
(1) after with the multiplying power charging 10h of 0.01C, then with the multiplying power progress constant-current charge of 0.05C, until voltage is 4.5V,
Stand 30min；Constant-current discharge is carried out extremely with the multiplying power of 0.05C, until voltage is 2.5V, stands 30min；
There are bulk gases in airbag for battery after chemical conversion, as shown in Figure 2；
Secondary encapsulation will be carried out to the lithium ion battery after chemical conversion, vacuumized, and carry out forming operation and obtain flexible packaged battery
Pond B1；
Performance test such as embodiment 1.
Comparative example 2
Flexible packing lithium ion battery B2, but this implementation as different from Example 5 is prepared in the method for repeating embodiment 5
Example uses traditional chemical conversion process, is melted into 25 DEG C of temperature, it is as follows to be embodied in process:
(1) constant-current charge is carried out with the multiplying power of 0.01C, until voltage is 4.9V, stands 30min；With the multiplying power of 0.05C into
Row constant-current discharge extremely, until voltage is 2.5V, stands 30min；
Secondary encapsulation will be carried out to the lithium ion battery after chemical conversion, vacuumized, and carry out forming operation and obtain flexible packaged battery
Pond B1；
Performance test such as embodiment 1.
The performance test results of above-described embodiment and comparative example are shown in Table shown in 1.
1 embodiment and comparative example the performance test results of table
As it can be seen from table 1 chemical synthesizing method of the invention it is more traditional chemical synthesizing method gas production it is significantly lower, thickness change
Very little, no flatulence happens, and battery capacity is higher, and 300 weeks conservation rates are significantly more excellent.
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, it is clear that those skilled in the art
Various changes and modifications can be made to the invention by member without departing from the spirit and scope of the present invention.If in this way, of the invention
Within the scope of the claims of the present invention and its equivalent technology, then the present invention is also intended to encompass these to these modifications and variations
Including modification and variation.
Claims (7)
1. a kind of chemical synthesizing method of lithium ion battery, the cathode active material of the lithium ion battery contain lithium-rich manganese-based anode material
Material, the chemical synthesizing method include at least charge and discharge cycles three times, which is characterized in that the charge cutoff electricity of preceding charge and discharge cycles twice
It forces down in 4.4V, discharge current is greater than charging current and second of charging current is greater than first time charging current；Last time is filled
The charge cutoff voltage of discharge cycles is not less than 4.4V, and charging current is not less than the charging current of second of charge and discharge cycles；
The chemical synthesizing method the following steps are included:
Step 1, to lithium ion battery with electric current I0Constant-current charge 0-10h, then with electric current I1Carry out onstant current voltage limiting to charge, cut-off electricity
Press V1；With electric current D1Constant-current discharge, until voltage is V1ˊ, and meet following condition:
0.005C≤I0≤ 0.1C, 0.005C≤I1≤ 0.2C, 4.1V≤V1< 4.4V, and
I1< D1≤ 1.0C, 2.0V≤V1ˊ≤2.8V；
Step 2, with electric current I2Carry out onstant current voltage limiting to charge, blanking voltage V2；With electric current D2Constant-current discharge, until voltage is V2ˊ, and it is full
The following condition of foot:
I1< I2≤0.2C,V1≤V2< 4.4V, and
I2< D2≤ 1.0C, 2.0V≤V2ˊ≤2.8V；
Step 3 ... n-1, with electric current I3……In-1Carry out onstant current voltage limiting to charge, blanking voltage V3……Vn-1；With electric current
D3……n-1Constant-current discharge, until voltage is V3ˊ……Vn-1ˊ, and meet following condition:
I2≤I3……In-1≤0.2C,V2≤V3……Vn-1≤Vn, and
I3……In-1< D3……Dn-1≤ 1.0C, 2.0V≤V3ˊ……Vn-1ˊ≤2.8V, n >=3；
Step n, with electric current InCarry out onstant current voltage limiting to charge, blanking voltage Vn；With electric current DnConstant-current discharge, until voltage is Vnˊ, and it is full
The following condition of foot:
I2≤In≤ 0.2C, 4.4V≤Vn≤ 4.8V, and
In< Dn≤ 1.0C, 2.0V≤Vnˊ≤2.8V, n >=3.
2. chemical synthesizing method according to claim 1, which is characterized in that electric current I1,2Range be 0.01C-0.2C, cut-off electricity
Press V1,2Range be 4.20V-4.35V.
3. chemical synthesizing method according to claim 1, which is characterized in that electric current D1,2Range be 0.01C-0.5C, cut-off electricity
Press V ˊ1,2Range be 2.0-2.5V.
4. chemical synthesizing method according to claim 1, which is characterized in that electric current I3……InRange be 0.01C-0.2C, cut
Only voltage VnRange be 4.45V-4.8V.
5. chemical synthesizing method according to claim 1, which is characterized in that electric current D3……DnRange be 0.01C-0.5C, cut
Only voltage V ˊ3……VˊnRange be 2.0-2.5V.
6. chemical synthesizing method according to claim 1-5, which is characterized in that it is characterized in that, the step of the chemical conversion
Suddenly it is carried out in the environment of 0-60 DEG C.
7. a kind of lithium ion battery is greater than including anode, cathode and the diaphragm being placed between positive electrode and negative electrode, charge cutoff voltage
4.3V and be less than or equal to 5.0V, which is characterized in that using the chemical conversion side of lithium ion battery described in any one of claims 1-6
Method.
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| US11695104B2 (en) * | 2019-08-23 | 2023-07-04 | Enevate Corporation | Method and system for improved performance of silicon anode containing cells through formation |
| CN108631018B (en) * | 2018-04-27 | 2020-01-10 | 贵州中伟资源循环产业发展有限公司 | Method for preparing lithium ion battery by utilizing recovered resources |
| WO2019230464A1 (en) * | 2018-05-29 | 2019-12-05 | パナソニックＩｐマネジメント株式会社 | Charging method for nonaqueous electrolyte secondary cell and charging system for nonaqueous electrolyte secondary cell |
| CN109817868B (en) * | 2018-12-25 | 2022-05-03 | 中国电子科技集团公司第十八研究所 | High-voltage and high-safety lithium ion battery and preparation method thereof |
| CN111384457A (en) * | 2018-12-28 | 2020-07-07 | 安普瑞斯（南京）有限公司 | Formation method for improving first charge-discharge efficiency of lithium ion battery |
| FR3095552B1 (en) * | 2019-04-25 | 2021-04-02 | Renault Sas | Method of forming a Li-ion battery cell |
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| CN110323506B (en) * | 2019-07-11 | 2020-12-22 | 广州明美新能源股份有限公司 | Formation stabilizing method for lithium ion battery before storage |
| CN112242575A (en) * | 2019-07-16 | 2021-01-19 | 安徽盟维新能源科技有限公司 | Formation method of lithium metal battery and manufacturing method of lithium metal battery |
| CN112005426B (en) * | 2019-10-21 | 2023-03-10 | 宁德新能源科技有限公司 | Charging method, electronic device, and storage medium |
| CN110797579B (en) * | 2019-11-07 | 2021-08-24 | 蒋子杰 | Formation method of flexible package lithium ion battery with ternary material as anode |
| CN111293349B (en) * | 2020-02-19 | 2021-07-02 | 江西迪比科股份有限公司 | Formation method of lithium ion battery |
| CN113497288B (en) * | 2020-03-19 | 2022-12-13 | 宁德新能源科技有限公司 | Charging method, electronic device, and storage medium |
| CN111740178A (en) * | 2020-05-27 | 2020-10-02 | 天津力神电池股份有限公司 | Method for improving electrical performance of lithium-rich manganese-based lithium ion battery |
| CN113871737A (en) * | 2020-06-30 | 2021-12-31 | 北京卫蓝新能源科技有限公司 | Lithium ion battery activation method containing lithium-rich manganese-based material and obtained lithium ion battery |
| CN113948782B (en) * | 2020-07-16 | 2024-02-27 | 北京卫蓝新能源科技有限公司 | Method for inhibiting gas production of lithium-rich manganese-based battery under high voltage |
| CN114039099B (en) * | 2021-11-02 | 2023-06-30 | 远景动力技术(江苏)有限公司 | Lithium ion battery formation method and application thereof |
| CN114267893A (en) * | 2021-12-21 | 2022-04-01 | 欣旺达电动汽车电池有限公司 | Capacity grading activation method for lithium ion battery |
| CN114335772A (en) * | 2021-12-30 | 2022-04-12 | 山东聚信新能源科技有限公司 | Formation method for improving cycle performance of narrow-strip-shaped flexible package lithium ion battery |
| CN116190827B (en) * | 2022-12-06 | 2024-04-19 | 安徽格兰科新材料技术有限公司 | Method for shortening formation time of lithium ion battery |
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| CN101777669A (en) * | 2010-02-02 | 2010-07-14 | 江西联威新能源有限公司 | Precharging formation method for lithium ion battery |
| CN103647115B (en) * | 2013-12-18 | 2016-05-11 | 中国科学院宁波材料技术与工程研究所 | A kind of application process taking lithium-rich manganese-based solid-solution material as anodal battery |
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