CN102856532A - Preparation method of lithium-rich anode strip of lithium ion battery - Google Patents
Preparation method of lithium-rich anode strip of lithium ion battery Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion batteries and especially relates to a preparation method of a lithium-rich anode strip of a lithium ion battery. The preparation method comprises the following steps of 1, coating anode slurry on an anode current collector and drying to obtain an anode strip which comprises an anode diaphragm and needs lithium supplement, and 2, wetting the anode strip needing lithium supplement by an electrolyte until the anode diaphragm is wetted fully, and carrying out dual-channel contact between the anode diaphragm and lithium metal to obtain a lithium-rich anode strip, wherein in contact, a temperature is in a range of 10 to 150 DEG C and pressure intensity is less than 100MPa and contact time is less than 10 hours. Compared with the prior art, the preparation method has the advantages that an ion channel and an electron channel between lithium metal and the anode diaphragm can be formed simultaneously; a potential difference between an anode material and lithium metal can promote fast ionization of lithium metal so that lithium ions are formed; and the formed lithium ions are transferred and embed into anode active substance particles so that fast lithium supplement is realized. The preparation method has simple processes and can realize industrial batch production easily.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly the preparation method of the rich lithium anode sheet of a kind of lithium ion battery.
Background technology
1991, the creationary employing material with carbon element of Sony corporation of Japan was as lithium ion battery anode material, for having brought revolutionary variation in the lithium ion battery field.Since then, the fast development of lithium-ion electric pool technology is in mobile phone, video camera, notebook computer and other in a large number utilizations above portable electronics.Lithium ion battery has plurality of advantages, high such as voltage, volume is little, quality is light,, memory-less effect higher than ability, pollution-free, self discharge is little and have extended cycle life etc., is 21st century desirable movable electrical appliances power supply, electric car power supply and electricity storage station electrical storage device.
But the development of microminiaturized and long standby along with portable electric appts, these equipment to the proposition of the energy density of lithium ion battery more and more higher requirement.For existing anode material, in the initial charge process, all can form solid electrolyte film (SEI film), thereby consume a part from the lithium ion in the positive electrode, finally cause the first enclosed pasture efficient of battery core to be lower than 100%.For example the first enclosed pasture efficient of graphite material is about 90%, and alloy anode efficient is lower first, take the silicon anode material as example, it is first between the enclosed pasture efficient between 65% ~ 85%.For the energy density of by a relatively large margin raising battery core, just be necessary to improve the first enclosed pasture efficient of battery core.
Improve the first purpose of enclosed pasture efficient of battery core in order to reach, the expert has all launched the research of wide model both at home and abroad, and obtained some achievements: publication number is that the Chinese patent application of CN1290209C is mentioned lithium metal, anode material and on-aqueous liquid mixed-shaped form slurry, slurry is coated on the collector, then dry slurries; Although the method can play the lithium effect of mending, the final first purpose of coulomb efficient that realizes improving battery core, the production technology of whole battery core must be finished in hothouse, and lithium metal and anode material blend difficulty are large simultaneously, so production cost is higher.Application number is that the Japanese patent application employing of JP1996027910 covers the anode strip surface with metal lithium sheet, then reel and make battery, the method of pouring into again electrolyte prepares lithium ion battery, when using the method to mend lithium, behind the battery core assembled formation, metal lithium sheet is easy to pierce through barrier film and causes the anode and cathode short circuit; Simultaneously, owing to being difficult to prepare thinner metal lithium sheet, therefore often cause the amount of the lithium that anode strip can absorb to be far smaller than the lithium that metal lithium sheet provides, so that the problems such as lithium, cycle performance be poor appear analysing in battery core.
In view of this, necessaryly provide a kind of technique simple, with low cost and can effectively control the benefit lithium amount of antianode sheet and mend the preparation method of the rich lithium anode sheet of the inhomogeneity lithium ion battery of lithium, adopt the first enclosed pasture efficient that the method can the Effective Raise battery core, thereby the energy density of raising battery core by a relatively large margin, the while can also guarantee security performance and the cycle performance of battery.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, and provide a kind of technique simple, with low cost and can effectively control the benefit lithium amount of antianode sheet and mend the preparation method of the rich lithium anode sheet of the inhomogeneity lithium ion battery of lithium, adopt the first enclosed pasture efficient that the method can the Effective Raise battery core, thereby the energy density of raising battery core by a relatively large margin, can also guarantee simultaneously security performance and the cycle performance of battery, complicated to overcome benefit lithium method technique of the prior art, cost is higher, can not effectively control the lithium amount of mending, fail safe is not enough, and might cause the deficiency of the cycle performance variation of battery.
In order to achieve the above object, the present invention adopts following technical scheme.The preparation method of the rich lithium anode sheet of a kind of lithium ion battery, may further comprise the steps: step 1, anode slurry is coated on the anode collector, oven dry, make the anode strip of the lithium to be mended that comprises the anode diaphragm, wherein, the ambient humidity in the whole preparation process is less than 3%, and this after the anode strip of mending lithium can be for oven dry, cold pressing front, cold pressing after, behind the itemize or the anode pole piece behind the soldering polar ear.
Step 2, infiltrate the anode strip of the lithium to be mended that the first step makes with electrolyte, after the anode diaphragm is fully infiltrated, the anode diaphragm is contacted with the lithium metal binary channels, thereby between anode diaphragm and lithium metal, form electric current, lithium ion is embedded the anode diaphragm from lithium metal, obtain rich lithium anode sheet, wherein, the temperature during contact is 10 ~ 150 ℃, pressure is less than 100MPa, and the time is less than 10h.
As a kind of improvement of the preparation method of the rich lithium anode sheet of lithium ion battery of the present invention, the concentration of lithium ion is 0.01 ~ 3mol/L in the described electrolyte of step 2.In addition, can also regulate the viscosity of electrolyte, the kind of additive and the content of additive.By regulating lithium salt, electrolyte viscosity and additive types and content, can effectively regulate the formation speed of SEI film and lithium ion from the transmission speed of lithium metal anode active material particle inside; Thereby so that battery core forms better SEI film, has better chemical property.
As a kind of improvement of the preparation method of the rich lithium anode sheet of lithium ion battery of the present invention, the water content of the anode diaphragm in the anode strip of the described lithium to be mended of step 1 is no more than 300ppm.Because lithium metal is more active, if the water content in the anode strip of lithium to be mended is too high, meeting causes the safety problems such as burning, blast so that lithium metal and steeping in water for reconstitution are given birth to reaction, the carrying out that impact is produced.
As a kind of improvement of the preparation method of the rich lithium anode sheet of lithium ion battery of the present invention, the described binary channels contact of step 2 contacts with ion channel for electron channel contacts.
As a kind of improvement of the preparation method of the rich lithium anode sheet of lithium ion battery of the present invention, described electron channel contact directly contacts the electron propagation ducts of formation for anode diaphragm and lithium metal.
As a kind of improvement of the preparation method of the rich lithium anode sheet of lithium ion battery of the present invention, described ion channel contact for the anode diaphragm by the lithium ion transmission channel of electrolyte with lithium metal indirect contact formation.When lithium ion passage and electron channel are communicated with simultaneously, the electrical potential difference that itself exists between the anode material that applies on the anode strip and the lithium metal can impel the quick ionization of lithium metal to form lithium ion, embed the anode active material granule interior by the electrolyte transmission, finally reach the purpose of fast repairing lithium.
As a kind of improvement of the preparation method of the rich lithium anode sheet of lithium ion battery of the present invention, the described lithium metal of step 2 is metal lithium bands.Metal lithium bands is lithium metal macroscopic body, therefore need not lithium metal and anode slurry blend, and method technique is simple, and is with low cost, very easily realizes industrialized mass production.
As a kind of improvement of the preparation method of the rich lithium anode sheet of lithium ion battery of the present invention, the Contact Temperature of the described anode diaphragm of step 2 and lithium metal is 25 ~ 100 ℃, and contact is 0.001 ~ 10MPa, and be 1s ~ 10min time of contact, and this is preferred scope.
As a kind of improvement of the preparation method of the rich lithium anode sheet of lithium ion battery of the present invention, the Contact Temperature of the described anode diaphragm of step 2 and lithium metal is 50 ℃, and contact is 2MPa, and be 2min time of contact, and this is better selection.
Compared with prior art, the preparation method of the rich lithium anode sheet of lithium ion battery of the present invention has following advantage at least.
First, the present invention need to be before mending lithium, allow the anode diaphragm fully be infiltrated by electrolyte, then with lithium metal and anode diaphragm Surface Contact, at this moment, electrolyte is joined together to form ion channel with lithium metal and anode diaphragm, and lithium metal and anode diaphragm directly are joined together to form electron channel, when lithium ion passage and electron channel are communicated with simultaneously, be equivalent between lithium metal and anode diaphragm, form electric current, and the electrical potential difference that itself exists between the anode material on the anode diaphragm and the lithium metal can impel the quick ionization of lithium metal to form lithium ion, lithium ion embeds the anode active material granule interior by the electrolyte transmission again, finally reaches the purpose of fast repairing lithium.
The second, the operating procedure aspect, the temperature and pressure when the present invention can very simply contact with the anode diaphragm by the control lithium metal, thus the control lithium ion is from the transmission speed of lithium metal anode active material particle inside; The time that contacts with the anode diaphragm by controlling lithium metal, thereby the control lithium ion is from the transmission time of lithium metal anode active material particle inside, final very simply the realization mending the control of lithium total amount, and realize the purpose that the anode diaphragm is evenly mended lithium, thereby the first enclosed pasture efficient of Effective Raise battery core, improve greatly the energy density of battery core, and prevent that the lithium metal that battery core occurs analysing lithium, separate out from piercing through the safety problem that the barrier film in the battery causes, guarantee the cycle performance of battery.Temperature when in a word, lithium metal contacts with the anode diaphragm is higher, pressure is larger, the longer lithium amount of then mending of time is more; But during excess Temperature, electrolyte decomposition speed is accelerated, thereby the antianode diaphragm causes very large destruction; And pressure is when larger, and the distortion of lithium metal is more serious, mend the lithium consistency and more be difficult to ensure card, and the destruction of antianode diaphragm is more serious; And the benefit lithium time is longer, and the production capacity of equipment is lower; Therefore after considering above factor, determined to mend the scope of temperature, pressure and time when lithium metal contacts with the anode diaphragm in the lithium process.
The 3rd, lithium used in the present invention is the larger macroscopical lithium metal of volume, need not lithium metal and anode slurry blend, and employed anode strip is the anode strip after applying simultaneously, so the method technique is simple, and is with low cost, very easily realizes industrialized mass production.
In addition, the present invention also provides the preparation method of the rich lithium anode sheet of another lithium ion battery, may further comprise the steps: step 1, anode slurry is coated on the anode collector, and dry, make the anode strip of the lithium to be mended that comprises the anode diaphragm; Step 2, infiltrate the anode strip of the lithium to be mended that the first step makes with electrolyte, after the anode diaphragm is fully infiltrated, between anode diaphragm and lithium metal, barrier film is set, between anode diaphragm and lithium metal, switch on again, between anode diaphragm and lithium metal, form electric current, lithium ion is embedded the anode diaphragm from lithium metal, obtain rich lithium anode sheet.This just is equivalent to the anode strip of lithium to be mended and lithium metal have been assembled into a battery, then transmission embeds the anode active material granule interior through electrolyte to make lithium ion by energising, finally reach the purpose of fast repairing lithium, its essence also is a kind of method that makes lithium ion embed the anode active material granule interior.
With respect to prior art, the present invention is simple to operate, only need between anode diaphragm and lithium metal, to arrange the benefit lithium operation that barrier film is switched on and just can be realized the anode diaphragm, and by control electrical current size and just can control simply and effectively the benefit lithium amount of thinking the anode diaphragm conduction time, and the method for energising is so that the benefit lithium is more even, thereby the first enclosed pasture efficient of Effective Raise battery core, improve greatly the energy density of battery core, and prevent that lithium from appearring analysing in battery core, the lithium metal of separating out pierces through the safety problem that the barrier film in the battery causes, and guarantees the cycle performance of battery.
Embodiment
Describe the present invention and beneficial effect thereof in detail below in conjunction with specific embodiment, still, embodiments of the invention are not limited to this.
Embodiment 1:The present embodiment provides the preparation method of the rich lithium anode sheet of a kind of lithium ion battery, may further comprise the steps: step 1, anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is graphite) be coated on the anode collector, oven dry, so that the water content of anode diaphragm is no more than 300ppm, make the anode strip of lithium to be mended.
Step 2, in hothouse, the anode strip of the lithium to be mended that the first step is made places electrolyte (lithium salt is 1mol/L), after the anode diaphragm is fully infiltrated, the anode diaphragm is contacted with the metal lithium bands binary channels, the temperature T during contact is 10 ℃, pressure P is 0, be 10h time of contact, so that the lithium-inserting amount in the graphite is 5% of graphite total capacity, obtains rich lithium anode sheet.
Embodiment 2:The present embodiment provides the preparation method of the rich lithium anode sheet of a kind of lithium ion battery, may further comprise the steps: step 1, anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is graphite) be coated on the anode collector, oven dry, so that the water content of anode diaphragm is no more than 300ppm, make the anode strip of lithium to be mended after colding pressing.
Step 2, in hothouse, the anode strip of the lithium to be mended that the first step is made places electrolyte (lithium salt is 0.1mol/L), after the anode diaphragm is fully infiltrated, the anode diaphragm is contacted with the metal lithium bands binary channels, the temperature T during contact is 70 ℃, pressure P is 0.2MPa, be 2h time of contact, so that the lithium-inserting amount in the graphite is 15% of graphite total capacity, obtains rich lithium anode sheet.
Embodiment 3:The present embodiment provides the preparation method of the rich lithium anode sheet of a kind of lithium ion battery, may further comprise the steps: step 1, anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is silicon) be coated on the anode collector, oven dry, so that the water content of anode diaphragm is no more than 300ppm, again through colding pressing and itemize after make the anode strip of lithium to be mended.
Step 2, in hothouse, the anode strip of the lithium to be mended that the first step is made places electrolyte (lithium salt is 2mol/L), after the anode diaphragm is fully infiltrated, the anode diaphragm is contacted with the metal lithium bands binary channels, the temperature T during contact is 150 ℃, pressure P is 10MPa, be 1min time of contact, so that the lithium-inserting amount in the silicon is 0.01% of silicon total capacity, obtains rich lithium anode sheet.
Embodiment 4:The present embodiment provides the preparation method of the rich lithium anode sheet of a kind of lithium ion battery, may further comprise the steps: step 1, anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is silicon) be coated on the anode collector, oven dry, so that the water content of anode diaphragm is no more than 300ppm, again through colding pressing, make behind itemize and the welding anode lug anode strip of lithium to be mended.
Step 2, in hothouse, the anode strip of the lithium to be mended that the first step is made places electrolyte (lithium salt is 0.5mol/L), after the anode diaphragm is fully infiltrated, the anode diaphragm is contacted with the metal lithium bands binary channels, the temperature T during contact is 100 ℃, pressure P is 0.6MPa, be 5h time of contact, so that the lithium-inserting amount in the silicon is 20% of silicon total capacity, obtains rich lithium anode sheet.
Embodiment 5:The present embodiment provides the preparation method of the rich lithium anode sheet of a kind of lithium ion battery, may further comprise the steps: step 1, anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is graphite) be coated on the anode collector, oven dry, so that the water content of anode diaphragm is no more than 300ppm, through after colding pressing, make the anode strip of lithium to be mended again.
Step 2, in hothouse, infiltrate the anode strip of the lithium to be mended that the first step makes with electrolyte (lithium salt is 0.01mol/L), after the anode diaphragm is fully infiltrated, the anode diaphragm is contacted with the metal lithium bands binary channels, the temperature T during contact is 30 ℃, pressure P is 100MPa, be 0.1s time of contact, so that the lithium-inserting amount in the graphite is 2% of graphite total capacity, obtains rich lithium anode sheet.
Embodiment 6:The present embodiment provides the preparation method of the rich lithium anode sheet of a kind of lithium ion battery, may further comprise the steps: step 1, anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is graphite) be coated on the anode collector, oven dry, so that the water content of anode diaphragm is no more than 300ppm, again through colding pressing and itemize after make the anode strip of lithium to be mended.
Step 2, in hothouse, the anode strip of the lithium to be mended that the first step is made places electrolyte (lithium salt is 3mol/L), after the anode diaphragm is fully infiltrated, the anode diaphragm is contacted with the metal lithium bands binary channels, the temperature T during contact is 50 ℃, pressure P is 50MPa, be 3min time of contact, so that the lithium-inserting amount in the graphite is 5% of graphite total capacity, obtains rich lithium anode sheet.
Embodiment 7:The present embodiment provides the preparation method of the rich lithium anode sheet of a kind of lithium ion battery, may further comprise the steps: step 1, anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is the mixture of graphite and silicon, the mass ratio of the two is respectively 4:1) be coated on the anode collector, oven dry so that the water content of anode diaphragm is no more than 300ppm, again through colding pressing and itemize after make the anode strip of lithium to be mended.
Step 2, in hothouse, infiltrate the anode strip of the lithium to be mended that the first step makes with electrolyte (lithium salt is 1.5mol/L), after the anode diaphragm is fully infiltrated, the anode diaphragm is contacted with the metal lithium bands binary channels, the temperature T during contact is 80 ℃, pressure P is 20MPa, be 20min time of contact, so that the lithium-inserting amount in the anode active material is 12% of anode active material total capacity, obtains rich lithium anode sheet.
Embodiment 8:The present embodiment provides the preparation method of the rich lithium anode sheet of a kind of lithium ion battery, may further comprise the steps: step 1, anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is graphite) be coated on the anode collector, oven dry, so that the water content of anode diaphragm is no more than 300ppm, again through colding pressing and itemize after make the anode strip of lithium to be mended.
Step 2, in hothouse, the anode strip of the lithium to be mended that the first step is made places electrolyte (lithium salt is 2.5mol/L), after the anode diaphragm is fully infiltrated, the anode diaphragm is contacted with the metal lithium bands binary channels, the temperature T during contact is 120 ℃, pressure P is 5MPa, be 6min time of contact, so that the lithium-inserting amount in the graphite is 8% of graphite total capacity, obtains rich lithium anode sheet.
Embodiment 9:The present embodiment provides the preparation method of the rich lithium anode sheet of a kind of lithium ion battery, may further comprise the steps: step 1, anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is graphite) be coated on the anode collector, oven dry, so that the water content of anode diaphragm is no more than 300ppm, again through colding pressing and itemize after make the anode strip of lithium to be mended.
Step 2, in hothouse, the anode strip of the lithium to be mended that the first step is made places electrolyte, after the anode diaphragm is fully infiltrated, between anode diaphragm and metal lithium bands barrier film is set, then anode diaphragm, metal lithium bands and membrane winding are in the same place, and apply the charging current of 0.1C between anode diaphragm and metal lithium bands, uncoiling after the charging 1h obtains lithium-inserting amount in the graphite and is 10% rich lithium anode sheet of graphite total capacity.
Embodiment 10:The present embodiment provides the preparation method of the rich lithium anode sheet of a kind of lithium ion battery, may further comprise the steps: step 1, anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is silicon) be coated on the anode collector, oven dry, so that the water content of anode diaphragm is no more than 300ppm, again through colding pressing and itemize after make the anode strip of lithium to be mended.
Step 2, in hothouse, the anode strip of the lithium to be mended that the first step is made places electrolyte, after the anode diaphragm is fully infiltrated, between anode diaphragm and metal lithium bands barrier film is set, then anode diaphragm, metal lithium bands and membrane winding are in the same place, and apply the charging current of 0.5C between anode diaphragm and metal lithium bands, uncoiling after the charging 20min obtains lithium-inserting amount in the silicon and is 5% rich lithium anode sheet of silicon total capacity.
Comparative Examples 1:The preparation of the anode strip of this Comparative Examples comprises the steps: anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is graphite) be coated on the anode collector, oven dry, so that the water content of anode diaphragm is no more than 300ppm, again through colding pressing, making anode strip behind the itemize, welding anode lug.
Comparative Examples 2:The preparation of the anode strip of this Comparative Examples comprises the steps: anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is the mixture of silicon and graphite, the mass ratio of silicon and graphite is respectively 1:4) be coated on the anode collector, oven dry, so that the water content of anode diaphragm is no more than 300ppm, again through colding pressing, making anode strip behind the itemize, welding anode lug.
Comparative Examples 3:The preparation of the anode strip of this Comparative Examples comprises the steps: anode slurry (is comprised anode active material, bonding agent and conductive agent etc., wherein anode active material is silicon) be coated on the anode collector, oven dry, so that the water content of anode diaphragm is no more than 300ppm, again through colding pressing, making anode strip behind the itemize, welding anode lug.
Respectively the anode strip of embodiment 1 to 10 and Comparative Examples 1 to 3 and the mode of cathode sheets and barrier film process coiling are assembled into battery core, pass through afterwards closedtop, fluid injection (lithium salt is 1mol/L), leave standstill, change into the operations such as (capacity of changing into is ICC0), shaping and degasification, prepare lithium ion battery.Wherein, the battery number consecutively that the anode strip of employing embodiment 1 to 10 is made is S1-S10, and the battery number consecutively that the anode strip of employing Comparative Examples 1-3 is made is D1-D3.
In 35 ℃ of environment, by following flow process the battery that is numbered S1-S10 and D1-D3 is carried out volume test: at first leave standstill 3min; Then with the charging current constant current charge of 0.5C to 4.2V, constant voltage charge obtains charging capacity AGC0 to 0.05C again; Leave standstill 3min; Obtain first discharge capacity D0 with the discharging current constant-current discharge of 0.5C to 3.0V again; Finish volume test after leaving standstill 3min; The first enclosed pasture efficient of calculating afterwards battery core is: D0/ (ICC0+AGC0), acquired results is shown in table 1.
As can be seen from Table 1: the anode active material that is numbered the battery of S1, S2, S5, S6, S8 and S9 and D1 is graphite, and more several persons' first enclosed pasture efficient can be found out: the first enclosed pasture efficient after the rich lithium anode sheet that adopts method of the present invention to prepare is applied in the battery has obvious raising; The anode active material that is numbered the battery of S3, S4, S10 and D3 is silicon, result by D3 can find out, when adopting silicon as anode active material, battery first the enclosed pasture efficient lower, be 65% only, adopt method of the present invention that it is mended lithium after, even if be slight benefit lithium, the first enclosed pasture efficient of battery also is improved (seeing S3), mend lithium more after, the first enclosed pasture efficient of battery just can be greatly improved (seeing S4 and S10); The battery that is numbered S7 and D2 all adopts the mixture of silicon and graphite as anode active material, and the ratio of two kinds of active materials identical (silicon and graphite mass ratio be 1:4), relatively the first enclosed pasture efficient of the two can obviously be found out: the initial charge efficient of the raising battery that the rich lithium anode sheet that adopts method of the present invention to prepare can be larger.
Table 1: be numbered S1-S10 and D1-D3 battery the volume test result and first the enclosed pasture efficient.
| Numbering | ICC0+AGC0（mAh） | D0（mAh） | First the enclosed pasture efficient |
| S1 | 1578 | 1499 | 95% |
| S2 | 1578 | 1578 | 100% |
| S3 | 2308 | 1500.2 | 65.01% |
| S4 | 2308 | 2123 | 92% |
| S5 | 1578 | 1562 | 99% |
| S6 | 1578 | 1568 | 99% |
| S7 | 1718 | 1598 | 93% |
| S8 | 1578 | 1568 | 99% |
| S9 | 1578 | 1546 | 98% |
| S10 | 2308 | 2077 | 90% |
| D1 | 1578 | 1420 | 90% |
| D2 | 1718 | 1460 | 85% |
| D3 | 2308 | 1500 | 65% |
In sum, adopt the rich lithium anode sheet of lithium ion battery of method preparation of the present invention, can be by controlling accurately time, temperature and the pressure of lithium metal and anode diaphragm Surface Contact, effectively control benefit is in the amount of the lithium ion of anode active material inside and the uniformity of mending lithium, thereby the first enclosed pasture efficient of Effective Raise battery core, improve greatly the energy density of battery core, and prevent that the lithium metal that battery core occurs analysing lithium, separate out from piercing through the safety problem that the barrier film in the battery causes, and guarantee the cycle performance of battery.Simultaneously the raw material that uses of the method is the anode strip after applying, and the lithium metal that uses is larger-size lithium metal macroscopic body, so production technology is simple, and is with low cost, is easy to the industrialized mass battery core.
Need to prove, although the present invention only with graphite and the silicon ion as anode active material, those skilled in the art can also use some other anode material commonly used, silicon-carbon alloys for example, ashbury metal etc.
The preparation method of the rich lithium anode sheet of the lithium ion battery that the present invention proposes, be described by embodiment, person skilled obviously can be changed or suitably change and combination rich lithium anode preparation method of lithium ion battery as herein described within not breaking away from content of the present invention, spirit and scope, realizes the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are deemed to be included in spirit of the present invention, scope and the content.
Claims (10)
1. the preparation method of the rich lithium anode sheet of lithium ion battery is characterized in that, may further comprise the steps:
Step 1 is coated in anode slurry on the anode collector, dries, and makes the anode strip of the lithium to be mended that comprises the anode diaphragm;
Step 2, infiltrate the anode strip of the lithium to be mended that the first step makes with electrolyte, after the anode diaphragm is fully infiltrated, the anode diaphragm is contacted with the lithium metal binary channels, thereby between anode diaphragm and lithium metal, form electric current, lithium ion is embedded the anode diaphragm from lithium metal, obtain rich lithium anode sheet, wherein, the temperature during contact is 10 ~ 150 ℃, pressure is less than 100MPa, and the time is less than 10h.
2. the preparation method of the rich lithium anode sheet of lithium ion battery according to claim 1, it is characterized in that: the concentration of lithium ion is 0.01 ~ 3mol/L in the described electrolyte of step 2.
3. the preparation method of the rich lithium anode sheet of lithium ion battery according to claim 1, it is characterized in that: the water content of the anode diaphragm in the anode strip of the described lithium to be mended of step 1 is no more than 300ppm.
4. the preparation method of the rich lithium anode sheet of lithium ion battery according to claim 1, it is characterized in that: the described binary channels contact of step 2 contacts with ion channel for electron channel contacts.
5. the preparation method of the rich lithium anode sheet of lithium ion battery according to claim 4, it is characterized in that: described electron channel contact directly contacts the electron propagation ducts of formation for anode diaphragm and lithium metal.
6. the preparation method of the rich lithium anode sheet of lithium ion battery according to claim 4 is characterized in that: the lithium ion transmission channel that described ion channel contact forms by electrolyte and lithium metal indirect contact for the anode diaphragm.
7. the preparation method of the rich lithium anode sheet of lithium ion battery according to claim 1, it is characterized in that: the described lithium metal of step 2 is metal lithium bands.
8. the preparation method of the rich lithium anode sheet of lithium ion battery according to claim 1, it is characterized in that: the Contact Temperature of the described anode diaphragm of step 2 and lithium metal is 25 ~ 100 ℃, and contact is 0.001 ~ 10MPa, and be 1s ~ 10min time of contact.
9. the preparation method of the rich lithium anode sheet of lithium ion battery according to claim 8, it is characterized in that: the Contact Temperature of the described anode diaphragm of step 2 and lithium metal is 50 ℃, and contact is 2MPa, and be 2min time of contact.
10. the preparation method of the rich lithium anode sheet of lithium ion battery is characterized in that, may further comprise the steps:
Step 1 is coated in anode slurry on the anode collector, dries, and makes the anode strip of the lithium to be mended that comprises the anode diaphragm;
Step 2 infiltrates the anode strip of the lithium to be mended that the first step makes, after the anode diaphragm is fully infiltrated with electrolyte, between anode diaphragm and lithium metal, barrier film is set, between anode diaphragm and lithium metal, switch on again, lithium ion is embedded the anode diaphragm from lithium metal, obtain rich lithium anode sheet.
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| CN201210297148.7A Active CN102856532B (en) | 2012-08-21 | 2012-08-21 | A kind of preparation method of lithium-rich anode strip of lithium ion battery |
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| CN103560265A (en) * | 2013-11-06 | 2014-02-05 | 东莞新能源科技有限公司 | Lithium ion battery as well as lithium-rich positive piece and preparation method thereof |
| CN104201320A (en) * | 2014-09-16 | 2014-12-10 | 赵前永 | Method for pre-lithiating electrode material of lithium ion battery |
| CN104733783A (en) * | 2015-04-01 | 2015-06-24 | 广东烛光新能源科技有限公司 | Preparation method of lithium ion battery |
| CN104752773A (en) * | 2015-04-01 | 2015-07-01 | 广东烛光新能源科技有限公司 | Preparation method of lithium ion battery |
| CN105470450A (en) * | 2014-10-16 | 2016-04-06 | 万向A一二三系统有限公司 | Silicon negative electrode plate for lithium-ion power battery and preparation method of silicon negative electrode plate |
| CN107123785A (en) * | 2016-02-25 | 2017-09-01 | 宁德时代新能源科技股份有限公司 | Lithium system is mended to pole piece |
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| CN109713221A (en) * | 2018-12-27 | 2019-05-03 | 陕西煤业化工技术研究院有限责任公司 | A method of improving negative electrode of lithium ion battery performance |
| CN110178252A (en) * | 2017-08-10 | 2019-08-27 | 株式会社Lg化学 | The prelithiation method of cathode for secondary cell |
| CN111480251A (en) * | 2018-02-23 | 2020-07-31 | 株式会社Lg化学 | Negative electrode for lithium secondary battery, method for preparing same, and lithium secondary battery comprising same |
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| CN103199217A (en) * | 2013-04-02 | 2013-07-10 | 东莞新能源科技有限公司 | Lithium-rich pole piece of lithium ion battery and preparation method thereof |
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| CN104733783B (en) * | 2015-04-01 | 2017-03-29 | 广东烛光新能源科技有限公司 | A kind of preparation method of lithium ion battery |
| CN107123785A (en) * | 2016-02-25 | 2017-09-01 | 宁德时代新能源科技股份有限公司 | Lithium system is mended to pole piece |
| CN109256520A (en) * | 2017-07-12 | 2019-01-22 | 宁德时代新能源科技股份有限公司 | Anode sheet, secondary battery, and method for manufacturing anode sheet |
| CN110178252A (en) * | 2017-08-10 | 2019-08-27 | 株式会社Lg化学 | The prelithiation method of cathode for secondary cell |
| US11183683B2 (en) | 2017-08-10 | 2021-11-23 | Lg Chem, Ltd. | Pre-lithiation method of negative electrode for secondary battery |
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| CN111480251A (en) * | 2018-02-23 | 2020-07-31 | 株式会社Lg化学 | Negative electrode for lithium secondary battery, method for preparing same, and lithium secondary battery comprising same |
| CN111480251B (en) * | 2018-02-23 | 2023-09-26 | 株式会社Lg新能源 | Negative electrode for lithium secondary battery, method for producing same, and lithium secondary battery comprising same |
| CN113812018A (en) * | 2018-12-04 | 2021-12-17 | 株式会社Lg新能源 | Method for manufacturing negative electrode for lithium secondary battery |
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| CN113812018B (en) * | 2018-12-04 | 2024-10-25 | 株式会社Lg新能源 | Method for manufacturing negative electrode for lithium secondary battery |
| CN109713221A (en) * | 2018-12-27 | 2019-05-03 | 陕西煤业化工技术研究院有限责任公司 | A method of improving negative electrode of lithium ion battery performance |
| CN109713221B (en) * | 2018-12-27 | 2021-06-08 | 陕西煤业化工技术研究院有限责任公司 | Method for improving negative performance of lithium ion battery |
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