CN106299502B - The method for improving lithium ion battery energy density and cycle life - Google Patents
The method for improving lithium ion battery energy density and cycle life Download PDFInfo
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- CN106299502B CN106299502B CN201610796029.4A CN201610796029A CN106299502B CN 106299502 B CN106299502 B CN 106299502B CN 201610796029 A CN201610796029 A CN 201610796029A CN 106299502 B CN106299502 B CN 106299502B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of field of lithium ion battery, especially a kind of ferric phosphate lithium cell of high-energy；The object of the present invention is to provide a kind of capacity for improving ferric phosphate lithium cell, the practical gram specific capacity for playing lithium iron phosphate positive material, while the method for raising the ferric phosphate lithium cell energy density and cycle life that capacity will not decay in cyclic process；In lithium ion battery manufacturing process, addition supplements active lithium material formation mixing material in positive electrode active materials used, and gram specific capacity of mixing material improves, and supplements the active lithium amount that active lithium material is provided with 1-25% of the amount of effect active lithium for capacity of negative plates；The supplement activity lithium material will carry out de- lithium, take off structural breakdown after lithium, that is, until initial charge blanking voltage is set as the completely de- lithium to the voltage of irreversible state of the material when taking off lithium；It has the characteristics that concise in technology, easy to operate.
Description
Technical field
The present invention relates to a kind of field of lithium ion battery, especially a kind of lithium ion battery of high-energy.
Background technique
Lithium ion battery refers to the lithium ion battery using lithium ion battery as positive electrode, with its long-life, Gao An
The outstanding features such as total stability, wide operating temperature range, extensive material source are paid close attention to, especially power battery side for industry
Face.But lithium ion battery also has its disadvantage, mainly operating voltage is lower, only 3.2V, other opposite common lithium ions
For the 3.7V of positive electrode, the small 1.0~1.4g/cm of tap density3, this resulted in the energy density of lithium ion battery compared with
It is low, it is made 26650 cylindrical battery of highest monomer ferrous phosphate lithium battery model at present, energy density also only has 140.9wh/
Kg, battery capacity 3700mAh, weight 84g, voltage 3.2V.And it is required increasingly now for the energy density of lithium ion battery
Height, especially power battery, if the energy density of ferrous phosphate lithium battery does not continue to improve, market position will be by
To extreme influence, while the requirement to cycle life is also higher and higher.
The performance of lithium ion battery depends primarily on the simultaneous of positive and negative pole material selection, design proportion and itself and electrolyte etc.
Capacitive.Cathode graphite can all have certain excess i.e. general anode capacity/positive electrode capacity >=1.03 when battery design, guarantee activity
The insertion and abjection of lithium have enough positions, avoid the precipitation of lithium metal, to guarantee the safety and cycle life of battery.It is positive and negative
Can the matching of pole and electrolyte, especially cathode form stable solid-electrolyte interphace film with electrolyte and directly influence
The capacity of battery plays and the service life.Graphite cathode surface will form one layer of SEI film during the charging process, need to consume in film forming
A certain amount of active lithium, for the first charge discharge efficiency of graphite generally 90~95%, film forming needs to consume the 5%~11% of capacity of negative plates
Lithium.Discharge cut-off voltage will not be very low in cyclic process for battery simultaneously, in order to avoid over-discharge is caused, so the deintercalation ratio of high-order lithium
Example is considerably less, one can consider that this part lithium is stored in cathode and is not involved in removal lithium embedded substantially.Graphite cathode surface filming with
And the high-order lithium of storage derives from the active lithium of positive electrode, and the first charge discharge efficiency of lithium iron phosphate positive material is very high, base
, close to 100%, many materials can reach 155~163mAh/g for this, and graphite cathode, which forms active lithium required for SEI film, to be come
From in the reversible part of positive electrode, the practical capacity that plays of the anode of lithium ion battery is caused to reduce, generally only 125~
140mAh/g.For full battery, capacity has dropped 8%~14%, and the energy density for causing battery reduces.
Lithium ion battery after dissecting 1000 circulations, the lithium iron phosphate positive material gram specific capacity that this battery uses
159mAh/g, first charge discharge efficiency 98%, graphite cathode material gram specific capacity 350mAh/g, first charge discharge efficiency 92%, to after dissection just
Negative electrode material does the structural analyses such as XRD test, it has been found that positive and negative pole material structure is substantially unchanged, and capacity also exists.With following
Positive plate after ring makees button cell, using lithium piece as to electrode and reference electrode, 0.1C constant-current constant-voltage charging to 3.6V, cut-off
Electric current 0.01C, then with the current discharge of 0.1C to 2.5V, a gram specific capacity still has 159mAh/g, efficiency >=99%.Negative electrode material is also
So, make button cell with the negative electrode tab after circulation, using lithium piece as to electrode and reference electrode, with 0.1C, 0.05C, 0.02C,
0.01C ladder discharges into 0.005V, then with the electric current constant-current charge of 0.1C to 2.0V, gram specific capacity 350mAh/g, and efficiency >=
99%.This illustrates that the decaying of capacity in cyclic process is not due to positive and negative pole material structural damage and causes active lithium that can not take off
Caused by embedding, the decaying of capacity arises primarily at some side reactions of inside battery, the especially weight of negative terminal surface SEI film
It is whole, repair and thicken caused by active lithium be consumed, this phenomenon shows clearly, especially in the cyclic process of most initial
During it is high temperature circulation or stores, the capacity for taking around consumption 8~14% just can guarantee the stabilization of SEI film, hereafter
The capacity of lithium ion battery is constant with regard to kept stable.
So how to improve capacity and the service life of lithium ion battery, guarantee that the amount of Reversible Cycle lithium is vital；Needle
To problem above, it is badly in need of us and solves.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of capacity for improving lithium ion battery, especially
It is to improve the practical gram specific capacity played of positive electrode, while the raising lithium significantly decayed will not occur for capacity in cyclic process
The method of ion battery energy density and cycle life.
In order to achieve the above object, a kind of raising lithium ion battery energy density designed by the present invention and cycle life
Method, in lithium ion battery manufacturing process, addition supplements active lithium material and forms mixing material in positive electrode active materials used
Expect, gram specific capacity of mixing material improves, and supplementing active lithium material and being provided with the amount of effect active lithium is the 1-25% of capacity of negative plates
Active lithium amount；The supplement activity lithium material will carry out de- lithium, take off structural breakdown after lithium, that is, initial charge ends when taking off lithium
Until voltage is set as the completely de- lithium to the voltage of irreversible state of the material.
Supplementing active lithium material can be LiCoO2Or LiCrO2Or LiNiO2Or LiNixCoyMnzO2Or
LiNixCoyAlzO2Deng, and 0≤x, y, z≤1, x+y+z=1.
The Adding Way for supplementing active lithium material has very much, and supplementing active lithium material can be sintered in advance with positive electrode
Together, the phosphoric acid anode active material of lithium ion battery such as in the present embodiment is added after can premixing, can also directly with
Positive electrode mechanical mixture is used with for blended anode material, or is directly added during configuring anode sizing agent.
The production of anode slice of lithium ion battery in the present invention is that binder and solvent are first configured to glue, adds
Conductive agent is scattered, is eventually adding active material LiFePO4 and supplement active lithium material of lithium cobalt acid, is mixed into slurry, adjusts viscous
Degree reaches OK range, pole piece is coated with out on aluminium foil, roll-in cuts to obtain anode pole piece.
The production of cathode pole piece is that thickener and deionized water are first configured to glue, and addition conductive agent is scattered, then plus
Enter active material artificial graphite, finally plus bonding agent, is mixed into slurry, adjusts viscosity, pole piece is coated with out on copper foil.
Be fabricated to 26650 cylindrical battery, it is toasted after in the glove box of dew point < -50 DEG C fluid injection seal.
Battery is melted into after being shelved, and aging after being melted into for the first time, will will sufficiently recharge after gas recombination will be active
Lithium ion in lithium replenishers substance is sufficiently deviate from, using self-control internal pressure monitoring system real-time monitoring inner pressure of battery, partial volume system
Are as follows: 0.5C constant-current constant-voltage charging to 3.6V, cut-off current 0.02C, 0.5C constant-current discharge to 2.0V.
Charge cutoff voltage for the first time can be 4.2-5.2V, or do multiple circulation again, guarantee the complete of the pre- de- lithium of material
Entirely.
It is LiCoO when supplementing active lithium material2, anode in LiCoO2The weight ratio of addition is 1%-10%, supplement activity
The additive amount of lithium material is excessive than related to the amount for the effective active lithium that it is provided and capacity of negative plates, i.e. its effective active provided
It is 1%-25% that the amount of lithium, which accounts for capacity of negative plates, is converted into the ratio added in anode.The weight of LiCoO2 in anode is added
Ratio is 1-10%, be according to supplement capacity of negative plates 1-25% it is scaled come.
Has the characteristics that concise in technology, easy to operate according to the present invention as described hereinbefore.
Specific embodiment
With LiCoO in the embodiment of the present invention2For material as supplement active lithium, but innovative point of the invention is not limited to
LiCoO2, using LiFePO4 as positive electrode in the embodiment of the present invention, gram specific capacity 155-162mAh/g, first charge discharge efficiency
98.5-99.5%, for graphite material as negative electrode material, gram specific capacity is 350-360mAh/g, first charge discharge efficiency 93-95%.
LiCoO in the embodiment of the present invention2Additive amount be the 0.5~15% of active substances in cathode materials, it is more preferred
Range is 1-10%, additive amount and the amount for the effective active lithium that it is provided and capacity of negative plates excess in anode than related, i.e., its
It is 1-25% that the effective active lithium of offer, which accounts for capacity of negative plates, the adding proportion being converted into anode.
The production of anode pole piece in the present invention, first will be first by the solvent methyl of the binder of 2-5wt% and 80-120wt%
Pyrrolidones is configured to glue, scattered in the conductive agent that 1-5wt% is added, and is eventually adding active material LiFePO4 80-
The LiCoO of 95.5 and benefit lithium material 1-10wt%2, it is mixed into slurry, viscosity is adjusted, then on the aluminium foil of 0.01-0.016mm
It is coated with out pole piece, two-sided surface density 10-50mg/cm2, and roll-in cuts to obtain anode pole piece, compacted density 1.6-2.5g/cm3,
It is preferred that 2.1-2.4.
The production of cathode pole piece is: the thickener of 1-2wt% and deionized water being first configured to glue, 0.5- is added
The conductive black of 2wt% is scattered, adds the active material artificial graphite of 93-98wt%, finally plus the bonding of 2-4.4wt%
Agent is mixed into slurry, adjusts viscosity and reaches, and pole piece is coated with out on the copper foil of 0.008-0.010mm, cathode surface density is to correspond to just
Pole active material capacity is excessive to calculate gained surface density, and cathode pole piece compacted density 1.1-1.8g/cm than 5-30%3, cathode
Surface density excessively compares 10-25% to correspond to positive active material capacity.
The three layers of PP diaphragm for the diaphragm 0.012-0.025 that the present invention uses separate, and are fabricated to 26650 cylindrical battery, pass through
Fluid injection is sealed in < -50 DEG C of dew point of glove box after baking.
Battery is melted into after being shelved, aging after being melted into for the first time, and cut-off electricity will be fully recharged after gas recombination
Pressure is 4.45V-4.8, using self-control internal pressure monitoring system real-time monitoring inner pressure of battery, partial volume system of the invention are as follows: 0.5C is permanent
Constant-voltage charge is flowed to 3.6V, cut-off current 0.02C, 0.5C constant-current discharge to 2.0V.
Embodiment 1:
The present embodiment description a kind of raising lithium ion battery energy density and cycle life method, be with LiFePO4
Positive electrode active materials, gram specific capacity of LiFePO4 are 159mAh/g, first charge discharge efficiency 99%；With natural coated graphite cathode material
Material, gram specific capacity 360mAh/g, first charge discharge efficiency 94%；With LiCoO2As the active lithium material of supplement, LiCoO2With positive-active material
Material is added when being pre-sintered.
Wherein, the production of anode pole piece is: first by the solvent methyl pyrrolidones of the binder of 3wt% and 80-120wt%
It is configured to glue, it is scattered in the conductive agent that 2wt% is added, it is eventually adding the sour iron lithium and 3.5wt% of 91.5wt%
LiCoO2, it is mixed into slurry, viscosity is adjusted, pole piece, two-sided surface density 38mg/cm is then coated with out on the aluminium foil of 0.016mm2,
And roll-in cuts to obtain anode pole piece, compacted density 2.3g/cm3。
The production of cathode pole piece is: the thickener of 1.2wt% and deionized water being first configured to glue, 0.5wt% is added
Conductive black it is scattered, add the active material artificial graphite of 96.2wt%, finally plus the binder of 3.6wt%, mixing
It at slurry, adjusts viscosity and reaches, pole piece is coated with out on the copper foil of 0.010mm, cathode surface density is to correspond to positive active material appearance
Amount is excessive to calculate gained surface density, and cathode pole piece compacted density 1.5g/cm than 25%3。
Anode pole piece is separated with cathode pole piece using three layers of PP diaphragm of 0.02mm, and 26650 cylindrical battery is fabricated to, and is passed through
Fluid injection is sealed in < -50 DEG C of dew point of glove box after baking.
Battery is melted into after being shelved, aging after being melted into for the first time, and cut-off electricity will be fully recharged after gas recombination
Pressure is 4.5V, using self-control internal pressure monitoring system real-time monitoring inner pressure of battery, partial volume system of the invention are as follows: 0.5C constant current constant voltage
It is charged to 3.6V, cut-off current 0.02C, 0.5C constant-current discharge to 2.0V.
Embodiment 2:
The present embodiment description a kind of raising lithium ion battery energy density and cycle life method, be with LiFePO4
Positive electrode active materials, gram specific capacity of LiFePO4 are 159mAh/g, first charge discharge efficiency 98.5%；It is negative with natural coated graphite
Pole active material, gram specific capacity of artificial graphite are 360mAh/g, first charge discharge efficiency 94%；With LiCoO2As supplement active lithium
Material, and LiCoO2It is added with positive electrode active materials when being pre-sintered.
Wherein, the production of anode pole piece is: first by the solvent methyl pyrrolidones of the binder of 2wt% and 80-120wt%
It is configured to glue, it is scattered in the conductive agent that 1.5wt% is added, it is eventually adding the LiFePO4 and 7wt% of 89.5wt%
LiCoO2, it is mixed into slurry, viscosity is adjusted, pole piece, two-sided surface density 40mg/cm is coated with out on the aluminium foil of 0.016mm2, and roller
Pressure cutting obtains anode pole piece, compacted density 2.35g/cm3。
The production of cathode pole piece is: the thickener of 1.4wt% and deionized water being first configured to glue, 0.8wt% is added
Conductive black it is scattered, add the active material artificial graphite of 96wt%, finally plus the binder of 3.6wt%, be mixed into
Slurry adjusts viscosity, pole piece is coated with out on the copper foil of 0.010mm, cathode pole piece surface density is to correspond to positive active material appearance
Amount is excessive to calculate gained surface density, cathode compacted density 1.55g/cm than 20%3。
Anode pole piece is separated with cathode pole piece using three layers of PP diaphragm of 0.02mm, and 26650 cylindrical battery is fabricated to, and is passed through
Fluid injection is sealed in < -50 DEG C of dew point of glove box after baking.
Battery is melted into after being shelved, aging after being melted into for the first time, and cut-off electricity will be fully recharged after gas recombination
Pressure is 4.75V, using self-control internal pressure monitoring system real-time monitoring inner pressure of battery, partial volume system of the invention are as follows: 0.5C constant current is permanent
Pressure is charged to 3.6V, cut-off current 0.02C, 0.5C constant-current discharge to 2.0V.
Embodiment 3:
The present embodiment description using LiFePO4 as positive electrode active materials, gram specific capacity of LiFePO4 is 159mAh/g,
First charge discharge efficiency is 99%；Using artificial graphite as negative electrode active material, gram specific capacity of natural coated graphite is 355mAh/g, for the first time
Efficiency is 93%；With LiCoO2As supplementing active lithium material, and LiCoO2It is added after premix with positive electrode active materials.
Wherein, the production of anode pole piece is: first matching the solvent methyl pyrrolidones of the binder of 2wt% and 100wt%
It is set to glue, it is scattered in the conductive agent that 1wt% is added, it is eventually adding the LiFePO4 of 87wt% and the LiCoO of 10wt%2,
It is mixed into slurry, viscosity is adjusted, pole piece, two-sided surface density 38mg/cm is coated with out on the aluminium foil of 0.016mm2, and roll-in is cut
Obtain anode pole piece, compacted density 2.4g/cm3。
The production of cathode pole piece is: the thickener of 1.6wt% and deionized water being first configured to glue, 0.5wt% is added
Conductive black it is scattered, add the active material artificial graphite of 96.4wt%, finally plus the binder of 3wt%, be mixed into
Slurry adjusts viscosity, pole piece is coated with out on the copper foil of 0.010mm, cathode surface density is to correspond to positive active material capacity mistake
Amount calculates gained surface density, cathode compacted density 1.45g/cm than 18%3。
Anode pole piece is separated with cathode pole piece using three layers of PP diaphragm of 0.016mm, and 26650 cylindrical battery is fabricated to,
Fluid injection is sealed in < -50 DEG C of dew point of glove box after toasted.
Battery is melted into after being shelved, aging after being melted into for the first time, and cut-off electricity will be fully recharged after gas recombination
Pressure is 4.7V, using self-control internal pressure monitoring system real-time monitoring inner pressure of battery, partial volume system of the invention are as follows: 0.5C constant current constant voltage
It is charged to 3.6V, cut-off current 0.02C, 0.5C constant-current discharge to 2.0V.
Embodiment 4:
The present embodiment description with LiCoO2As the active lithium material of supplement, a gram specific capacity for LiFePO4 is
159mAh/g, first charge discharge efficiency 99%；Using natural coated graphite as negative electrode active material, a gram specific capacity for natural coated graphite is
360mAh/g, first charge discharge efficiency 94%；With LiCoO2As supplementing active lithium material, and LiCoO2With positive electrode active materials pre-
It is added after mixed.
Wherein, the production of anode pole piece is: first by the solvent methyl pyrrolidines of the binder of 4.5wt% and 80-120wt%
Ketone is configured to glue, scattered in the conductive agent that 1wt% is added, and is eventually adding the LiFePO4 and 2wt% of 94wt%
LiCoO2, it is mixed into slurry, viscosity is adjusted, pole piece, two-sided surface density 36mg/cm is coated with out on the aluminium foil of 0.016mm2, and roller
Pressure cutting obtains anode pole piece, compacted density 2.1g/cm3。
The production of cathode pole piece is: the thickener of 1.2wt% and deionized water being first configured to glue, 1.7wt% is added
Conductive black it is scattered, add the active material artificial graphite of 95.2wt%, finally plus the binder of 3.8wt%, mixing
At slurry, viscosity is adjusted, pole piece is coated with out on the copper foil of 0.010mm, cathode surface density is to correspond to positive active material capacity
It is excessive that gained surface density, cathode compacted density 1.35g/cm are calculated than 10%3。
Anode pole piece is separated with cathode pole piece using three layers of PP diaphragm of 0.02mm, and 26650 cylindrical battery is fabricated to, and is passed through
Fluid injection is sealed in < -50 DEG C of dew point of glove box after baking.
Battery is melted into after being shelved, aging after being melted into for the first time, and cut-off electricity will be fully recharged after gas recombination
Pressure is 4.65V, using self-control internal pressure monitoring system real-time monitoring inner pressure of battery, partial volume system of the invention are as follows: 0.5C constant current is permanent
Pressure is charged to 3.6V, cut-off current 0.02C, 0.5C constant-current discharge to 2.0V.
Embodiment 5:
The present embodiment description with LiCoO2As the active lithium material of supplement, using LiFePO4 as positive electrode active materials, phosphorus
Gram specific capacity of sour iron lithium is 159mAh/g, first charge discharge efficiency 99%；To be surface-treated graphite as negative electrode active material, at surface
Gram specific capacity 360mAh/g of fibrous gypsum ink, first charge discharge efficiency 94%.
The production of anode pole piece is: binder 2wt% and solvent methyl pyrrolidones 80-120wt% first being configured plastic
Liquid, being added, conductive agent 1wt% is scattered, is eventually adding active material LiFePO4 93.5wt% and mends lithium material cobalt acid lithium
1wt% is mixed into slurry, adjusts viscosity, pole piece, two-sided surface density 30mg/cm are coated with out on the aluminium foil of 0.0160mm2, and
Roll-in cuts to obtain anode pole piece, compacted density 2.0g/cm3。
The production of cathode pole piece is: thickener 1.2wt% and deionized water being first configured to glue, conductive black is added
1wt% is scattered, adds active material artificial graphite 96wt%, and last adding additives 3.6wt% is mixed into slurry, adjusts
Viscosity, is coated with out pole piece on the copper foil of 0.010mm, and cathode surface density is excessively compared in terms of 20% by corresponding to positive active material capacity
Calculate gained surface density, cathode compacted density 1.45g/cm3。
Anode pole piece is separated with cathode pole piece using three layers of PP diaphragm of 0.25mm, using the steel shell of 0.2mm wall thickness, through drying
Fluid injection is sealed in < -50 DEG C of dew point of glove box after roasting, is fabricated to 26650 cylindrical battery.
Battery is melted into after being shelved, aging after being melted into for the first time, and cut-off electricity will be fully recharged after gas recombination
Pressure is 4.65V, using self-control internal pressure monitoring system real-time monitoring inner pressure of battery, partial volume system of the invention are as follows: 0.5C constant current is permanent
Pressure is charged to 3.6V, cut-off current 0.02C, 0.5C constant-current discharge to 2.0V.
Comparative example 1:
This comparative example is using LiCoO2 as the active lithium material of supplement, using LiFePO4 as positive electrode, gram of LiFePO4
Specific capacity 159mAh/g, first charge discharge efficiency 99%, using natural coated graphite as negative electrode material, gram specific capacity of natural coated graphite
360mAh/g, first charge discharge efficiency 94%.
Anode pole piece production: being first configured to glue for 3wt% binder and 80~120wt% solvent methyl pyrrolidones,
It is scattered in the conductive agent that 2wt% is added, it is eventually adding the LiFePO4 of 94wt% and the LiCoO2 of 1wt%, is mixed into slurry,
It adjusts viscosity and reaches OK range, pole piece, two-sided surface density 36mg/cm2, and roll-in point are coated with out on the aluminium foil of 0.016mm
It cuts to obtain anode pole piece, compacted density 2.3g/cm3.
Cathode pole piece production: the thickener of 1.2wt% and deionized water are first configured to glue, leading for 0.5wt% is added
Electric carbon black dispersion is good, adds the active material graphite of 96.2wt%, finally plus the binder of 3.6wt%, is mixed into slurry, adjusts
Section viscosity reaches OK range, pole piece is coated with out on the copper foil of 0.010mm, cathode surface density is to correspond to positive active material appearance
Amount is excessive to calculate gained surface density, cathode compacted density 1.5g/cm3 than 25%.
Anode pole piece is separated with cathode pole piece using three layers of PP diaphragm of 0.25mm, and 26650 cylindrical battery is fabricated to, and is passed through
Fluid injection is sealed in < -50 DEG C of dew point of glove box after baking.
Battery is melted into after being shelved, aging after being melted into for the first time, and cut-off electricity will be fully recharged after gas recombination
Pressure is 4.3V, using self-control internal pressure monitoring system real-time monitoring inner pressure of battery.Partial volume system of the invention are as follows: 0.5C constant current constant voltage
It is charged to 3.6V, cut-off current 0.02C, 0.5C constant-current discharge to 2.0V.
Comparative example 2:
This comparative example is using LiFePO4 as positive electrode active materials, gram specific capacity 159mAh/g of LiFePO4, first charge discharge efficiency
99%, using natural coated graphite as negative electrode active material, gram specific capacity 360mAh/g of natural coated graphite, first charge discharge efficiency
94%.
Anode pole piece production: the solvent methyl pyrrolidones of the binder of 3.5wt% and 120wt% are first configured into plastic
Liquid, it is scattered in the conductive agent that 1.5wt% is added, it is eventually adding the LiFePO4 of 95wt%, is mixed into slurry, viscosity is adjusted and reaches
To OK range, pole piece, two-sided surface density 36mg/cm2 are coated with out on the aluminium foil of 0.016mm, and roll-in cuts to obtain anode
Pole piece, compacted density 2.25g/cm3。
Cathode pole piece production: the thickener of 1.2wt% and deionized water are first configured to glue, leading for 0.5wt% is added
Electric carbon black dispersion is good, adds the natural coated graphite of 96.2wt%, finally plus the binder of 3.6wt%, is mixed into slurry, adjusts
Section viscosity reaches OK range, is coated with out pole piece on the copper foil of 0.010mm.Cathode surface density is to correspond to positive active material appearance
Amount is excessive to calculate gained surface density, cathode compacted density 1.5g/cm than 25%3。
Anode pole piece is separated with cathode pole piece using three layers of PP diaphragm of 0.25mm, and 26650 cylindrical battery is fabricated to, and is passed through
Fluid injection is sealed in < -50 DEG C of dew point of glove box after baking.
Battery is melted into after being shelved, aging after being melted into for the first time, and cut-off electricity will be fully recharged after gas recombination
Pressure is 4.2V, using self-control internal pressure monitoring system real-time monitoring inner pressure of battery.Partial volume system of the invention are as follows: 0.5C constant current constant voltage
It is charged to 3.6V, cut-off current 0.02C, 0.5C constant-current discharge to 2.0V.
Be below embodiment 1-5 and comparative example 1-2 battery be melted into, partial volume, each scheme randomly selects 100 electricity
First charge discharge efficiency, capacity and the test of corresponding weight are done in pond, are averaged, capacity comparison see the table below:
Cycle life: because of limited time, the long term life time-consuming of normal temperature circulation is too long, we use high temperature acceleration and follow
Ring, 60 degree of lower decaying recycled are 10~12 times of the rate of decay under 25 degree of room temperature, and each scheme of battery after partial volume respectively takes 3
The only 1C/1C charge-discharge cycle under 60 degree of climatic chamber high temperature, charge and discharge system: 1C constant-current constant-voltage charging to 3.6V, cut-off electricity
0.02C, then 1C constant-current discharge are flowed to 2.0V, are calculated its conservation rate after cycle life 500 times, are averaged.
It can be seen that in embodiment 1-5 from above-mentioned contrast table, energy density has to be improved to some extent, with supplement
The additive amount of active lithium material, the ratio for the abjection lithium for supplementing active lithium material are related, wherein the ferrous phosphate of embodiment 1,2,3
The monomer energy density average value of lithium battery has been more than 150wh/Kg, uses the materials such as special steel shell, monomer in embodiment 5
Energy density is even more than 170wh/kg.
It can be seen that in embodiment 3 from above-mentioned contrast table, the active lithium material of supplement is more and plays completely, releases
A large amount of active lithium, so that active lithium about 200mAh higher than positive electrode capacity is stored in cathode, while cathode is excessively more, guarantees
Analysis lithium phenomenon will not be generated；While improving battery energy density, the service life of battery is effectively extended；It is followed with high temperature
The data of ring are analyzed (in conjunction with Japan about loop attenuation theory analysis), in 25 degree of 1C/1C cycle lives of common batteries room temperature
On the basis of 8000-12000 times, improve at least 5000 times；Simultaneously should pay attention to be not each producer LiFePO 4 electricity
The service life in pond, which has, so to be grown, in close relations with respective technique, Row control and formula.
Claims (2)
1. a kind of method for improving lithium ion battery energy density and cycle life, it is characterised in that: made in lithium ion battery
In the process, addition supplements active lithium material and forms mixing material in positive electrode active materials used, and positive electrode active materials are phosphorus
Sour iron lithium, content 87-94wt%, supplementing active lithium material is LiCoO2, content 1-10wt%, gram ratio of mixing material
Capacity improves, and supplements the active lithium amount that active lithium material is provided with 1-25% of the amount of effect active lithium for capacity of negative plates；The benefit
De- lithium will be carried out by filling active lithium material, take off structural breakdown after lithium, that is, it is complete to be set as the material for initial charge blanking voltage when taking off lithium
Until de- lithium to the voltage of irreversible state, active lithium material LiCoO is supplemented2When de- lithium, initial charge blanking voltage is in 4.45-
Between 4.8V, structure collapses, active lithium abjection amount 240-270mAh/g, material structure collapse after can not be embedded in lithium ion again,
That is the amount of lithium ions of Reversible Cycle is close to 0%.
2. a kind of method for improving lithium ion battery energy density and cycle life according to claim 1, feature exist
In: gram specific capacity for supplementing the active lithium of itself abjection of active lithium material is higher than LiFePO4 itself.
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| CN110294494B (en) * | 2019-07-25 | 2022-04-01 | 哈尔滨工业大学 | Lithium vanadate anode lithium supplement additive and application thereof |
| CN114122494A (en) * | 2020-08-31 | 2022-03-01 | 深圳新宙邦科技股份有限公司 | Lithium ion battery |
| CN112993412A (en) * | 2021-02-19 | 2021-06-18 | 芜湖天弋能源科技有限公司 | Preparation method of high-performance lithium iron phosphate battery |
| CN113839097B (en) * | 2021-08-24 | 2023-10-24 | 浙江超恒动力科技有限公司 | Preparation method of electric bicycle battery |
| WO2023070287A1 (en) * | 2021-10-25 | 2023-05-04 | 宁德新能源科技有限公司 | Positive electrode plate, electrochemical device, and electronic device |
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