CN101783424A - Method for pre-charging lithium ion battery - Google Patents
Method for pre-charging lithium ion battery Download PDFInfo
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- CN101783424A CN101783424A CN200910105010A CN200910105010A CN101783424A CN 101783424 A CN101783424 A CN 101783424A CN 200910105010 A CN200910105010 A CN 200910105010A CN 200910105010 A CN200910105010 A CN 200910105010A CN 101783424 A CN101783424 A CN 101783424A
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- 238000000034 method Methods 0.000 title claims abstract description 64
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 27
- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- 239000010941 cobalt Substances 0.000 claims description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 23
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 20
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract 1
- 239000013543 active substance Substances 0.000 abstract 1
- 229910002096 lithium permanganate Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 230000005611 electricity Effects 0.000 description 11
- 238000007086 side reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000029087 digestion Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005429 filling process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- MOLYXOOGDFTUJT-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O.[Co] Chemical compound [Li].[Mn](=O)(=O)(O)O.[Co] MOLYXOOGDFTUJT-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003001 Li-Ni-Co-Mn-O Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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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
- 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
The invention discloses a method for pre-charging a lithium ion battery of which positive active substances are mixed material of lithium cobaltate and nickel-cobalt lithium permanganate. The method adopts staged charge and comprises at least two charge steps, wherein the charge current of the second charge step is heavier than that of the first charge step, and the total pre-charging electric quantity of the first charge step and the second charge step is 15 to 35 percent of the total electric quantity of the lithium ion battery. The pre-charging method of the invention can greatly shorten the pre-charging time and greatly improve the production efficiency.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of method for pre-charging of lithium ion battery.
Background technology
The application of lithium ion battery is extensive day by day at present, the battery requirements amount constantly increases, and for the battery producer, will enhance productivity on the one hand and satisfy market demand, require on the other hand to improve and replenishment of process, when improving the quality of products, enhance productivity.Along with the production mechanization of lithium electricity industry, the preliminary filling operation has become the key link of present restriction throughput rate and product quality.
Concerning lithium ion battery, when preliminary filling is primary charging, because electrochemical reaction, form the passivation thin layer that covers carbon electrodes inevitably on the boundary of carbon negative pole and electrolyte, this thin layer is solid electrolyte interface (solid electrolyte interface) or claims the SEI film.The process that lithium ion battery is carried out initial charge is also referred to as and changes into.In the battery formation process, when negative terminal surface generates the SEI film, side reaction can take place produce gaseous product.The gas that produces needs in time to discharge electric core, otherwise these gases gather at inside battery and can cause cell expansion, shell swell, distortion, even can cause battery to be blasted.And if gas produces not exclusively in the formation process, in the electric cyclic process in electric core later stage, can continue to emit, have a strong impact on the electrical property and the security performance of electric core.Therefore the step that changes into of lithium ion secondary rechargeable battery is to make the important stage of battery, is related to many-sided qualities such as capacity height, cycle life length, security performance of battery.
And the formation process of present stage normally adopts little electric current to reach tens hours charging, obtains desirable SEI film with expectation, keeps battery performance stable.But, change into step for a long time and cause production efficiency low.
The positive electrode of the extensive use of lithium ion battery at present is LiCoO
2But cobalt toxicity is bigger, and cobalt resource is rare, cost an arm and a leg, poor safety performance etc., above-mentioned these drawbacks limit LiCoO
2Further application, therefore because the emphasis that the cost performance better material becomes research is sought in the promotion of the economy of energy.Wherein, characteristics such as Li-Ni-Co-Mn-O series ternary material has height ratio capacity, stable cycle performance, cost is relatively low, security performance is better are considered to best and can replace LiCoO
2Positive electrode.Though cobalt acid lithium remains the leading role of ion battery, along with the commercialization of nickel-cobalt-manganese ternary material, more and more is subjected to the favor of battery manufacturer, in the near future, will be the epoch of nickel-cobalt-manganese ternary material.
Along with to the deepening continuously and the progress of battery manufacturing process of nickel-cobalt-manganese ternary material property research, it is extensive that the use of this material becomes gradually.But because the electrochemical reaction speed of this material is slow under the room temperature, cause the high rate during charging-discharging of this material not good, the research of relevant such material of great majority all adopts low range to charge and discharge, lower multiplying power will have a strong impact on the application of this system material, therefore preliminary filling still adopts traditional cobalt acid lithium method for pre-charging promptly to adopt little electric current to charge for a long time, becomes the key link of this material system production efficiency of present restriction and properties of product.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide a kind of at the composite material with cobalt acid lithium and nickle cobalt lithium manganate be positive active material lithium ion battery, can improve the also very big shortening charging interval method for pre-charging lithium ion batteries of enhancing productivity of electric core performance.
For achieving the above object, the present invention has adopted following technical scheme:
The invention discloses a kind of composite material with cobalt acid lithium and nickle cobalt lithium manganate is the method for pre-charging lithium ion batteries of positive active material, the method for pre-charging of described lithium ion battery is to adopt stage charging, described stage charging comprises at least two charge step, the charging current of second charge step is greater than the charging current of first charge step, and total preliminary filling electric weight of first charge step and second charge step is 15%～35% of the total electric weight of described lithium ion battery.
Preferably, total preliminary filling electric weight of first charge step and second charge step is 15%～30% of the total electric weight of described lithium ion battery.
In the positive active material of described lithium ion battery, cobalt acid lithium accounts for 60%～80%, and nickle cobalt lithium manganate accounts for 20%～40%, and in the concrete execution mode of the present invention, preferred cobalt acid lithium accounts for 80%, and nickle cobalt lithium manganate accounts for 20%, described being weight percentage.
Preferably, the charging current of described first charge step is less than 0.1C, and the charging interval is 5～30min.Further preferred, the charging current of first charge step is 0.05C～0.1C, and the charging interval is 5～15min.
Perhaps preferred, the charging current of described second charge step is 0.3C～0.6C, and the charging interval is 10～60min.
Owing to adopted above technical scheme, the beneficial effect that the present invention is possessed is:
Adopting method for pre-charging of the present invention is that the lithium ion battery of positive active material carries out precharge to the composite material with cobalt acid lithium and nickle cobalt lithium manganate, electric core is reached and the suitable even more excellent electric property of electric core that adopts the long-time preliminary filling technology of traditional little electric current, greatly shortened simultaneously pre-charging time, also can shorten simultaneously the digestion time of electric core, improved production efficiency widely, simultaneously, the nickle cobalt lithium manganate ternary material that is embodied as of method for pre-charging of the present invention uses widely solid foundation is provided.
Description of drawings
Fig. 1 is the positive active material lithium ion battery that to be cobalt acid lithium mix by 8: 2 part by weight with nickle cobalt lithium manganate, and it adopts electric current is the charge graph of 0.1C, and abscissa is time (min), and ordinate is a magnitude of voltage.
Embodiment
The application of lithium ion battery is extensive day by day at present, the battery requirements amount constantly increases, and for the battery producer, will enhance productivity on the one hand and satisfy market demand, require on the other hand to improve and replenishment of process, when improving the quality of products, enhance productivity.Production mechanization along with lithium electricity industry, the preliminary filling operation has become the key link of present restriction throughput rate and product quality, the invention provides a kind of composite material at positive pole employing cobalt acid lithium and nickle cobalt lithium manganate is the method for pre-charging of active material, can enhance productivity greatly under the prerequisite that electric core performance gets a promotion.
The present invention is directed to the electric core of the composite material of cobalt acid lithium and nickle cobalt lithium manganate,, quickened the carrying out of side reaction in the SEI film forming process, thereby can reach the preliminary filling purpose in the short time by introducing the preliminary filling work step of big electric current as positive active material.
The present invention at first is determined by experiment the relation of preliminary filling electric weight and pre-charge pressure, voltage during then by film forming is determined the suitable electric weight of preliminary filling, at last again by a series of embodiment, introducing by big pre-charge work step, finish the side reaction of film forming in the short time, and obtain the product that combination property improves.
At first, investigating positive active material is that cobalt acid lithium and nickle cobalt lithium manganate mix in proportion at 8: 2, and the preliminary filling electric current is the charge graph of 0.1C, as shown in Figure 1.
According to 0.1C charging interval-magnitude of voltage curve chart, investigate the finished product electricity core performance of charge volume between 10% (60min), 20% (120min) and 30% (180min) (magnitude of voltage corresponds to 3.61V, 3.72V and 3.81V) respectively.Because the one-tenth membrane voltage of SEI film is 3.60V, in preliminary filling (changing into) process, though it is different because of formation voltage that negative terminal surface forms the key reaction meeting of SEI film, but when charging voltage reaches into membrane voltage 3.60V, the SEI film begins to form, and the carrying out along with reaction little by little changes its structure and performance in charging process thereafter.That is to say that by figure (1) as can be known, when charge capacity was 10%, because voltage surpasses 3.60V to reach 3.61V, the SEI film had just begun to form.For further whether checking film forming and side reaction thereof are fully finished, this patent earlier with electric core with 0.1C charge respectively 60min, 90min, 120min and 180min, make electric core preliminary filling electric weight 10%, 15%, 20% and 30%, investigate performances such as its capacity, size, internal resistance respectively, by investigating the result, the preliminary filling electric weight is at 10% o'clock, and insufficient because of film forming side reaction exhaust, electric core has size super thick and analyse bad phenomenon such as lithium.Therefore this patent adopt different preliminary filling electric currents in time between combination, make the preliminary filling electric weight at 15%-35%, cabinet magnitude of voltage under the difference between the preferred 15%-30% is investigated capacity (capacity performance), internal resistance, size and the cycle performance thereof of electric core.
The present invention adopts stage charging modes, comprises first charge step and second charge step.The first step adopts the be formed with positive role of little electric current to the SEI film, help improving electric core capacity, but the SEI membrane impedance that long low current charge can cause forming increases, thereby influence the multiplying power discharging property of finished product electricity core, the long production efficiency that also influences of time course, therefore the little electric current of the first step (in the 0.1C) short time (in the 30min), it is for stage preliminary filling mode, almost is negligible to the influence of electric core end properties.By figure (1) charging curve as can be known, 0.1C charge 5 minutes the time, voltage is 2.89V, and the variation of magnitude of voltage (rising) is very fast and be unsettled before this, thus, for the lower limit of first step low current charge time, if then be preferably 5 minutes, if then be preferably 10 minutes with the 0.05C charging with the 0.1C charging.Second step was introduced big electric current, the carrying out that the charging modes of big electric current can quicken side reaction, improve formation efficiency, but destroy the formation of SEI film easily and cause the deterioration of electric core performance, the preliminary filling cabinet uses big current stability and error all bigger simultaneously, therefore should select suitable charging current and charging interval.Big electric current is chosen between the 0.3C-0.6C in the method for pre-charging of the present invention, and the charging interval is adjusted according to the size of electric current, usually in 10～60min.For stage preliminary filling technology of the present invention, because first step electric current is little and the charging interval is shorter, therefore, the electric weight that the first step reached can be ignored, and the electric weight that will reach behind the big pre-charge of second step should be 15%～35% preferred about 15%～30% of total electric weight.
In addition, adopt method of the present invention to carry out preliminary filling can also reduce electric core when greatly reducing pre-charging time digestion time.The purpose of ageing is in order to make electrolyte fully soak into the pole piece the inside, thereby the electrolyte content of electric core residue electrolyte etc. is sealed in the polarization phenomena when guaranteeing to avoid preliminary filling and the loss of electrolyte, assurance, because traditional handicraft adopts disposable 100% fluid injection, and pre-charging time is long, therefore digestion time is long relatively, needs tens hours usually; After being adjusted into new preliminary filling technology of the present invention, fluid injection is at twice, annotates electrolyte liquid 80%～85% earlier, after-teeming electrolyte 15%～10% again behind the preliminary filling, though the second step current ratio is bigger, the time is short, therefore on this basis digestion time is also shortened, can foreshorten to 1～2h.
Below by specific embodiment the present invention is done further detailed description.To be cobalt acid lithium and nickle cobalt lithium manganate mix by 8: 2 part by weight for used electric core all is same batch of production in the specific embodiment of the invention and embodiment 1～16, the Comparative Examples 1,2 613048AM-1000mAh electricity core, positive active material; To be cobalt acid lithium and nickle cobalt lithium manganate mix by 6: 4 part by weight for used electric core all is another batch production in embodiment 17～21 and the Comparative Examples 3,4 613048AM-1000mAh electricity core, positive active material.Same batch of all embodiment electricity core has consistent both positive and negative polarity dressing amount, and electrode density adopts identical injecting electrolytic solution, and reservoir quantity keeps same fluid injection preliminary filling and seals experiment conditions such as cleaning.
Embodiment 1
The detailed process step is as follows: sample electricity core is carried out fluid injection first, and reservoir quantity is a technological requirement 85%, presses 0.05C, 10min with going up the preliminary filling cabinet behind electric core ageing 1～2h again; 0.3C, the method for pre-charging of 29min carries out preliminary filling, plays the cabinet measuring voltage then, after-teeming liquid 10% back is pushed and is finished and seal electric core once more, above process all carries out under identical humiture environment, temperature≤26 ℃; Humidity≤2%.Under room temperature environment, the electric core that has sealed is cleaned the back measurement size, wear out and after 6 days electric core is detected partial volume, the partial volume system is undertaken by parameter shown in the table 2.Investigate its capacity, internal resistance, 3.92V size and cycle performance test, the results are shown in Table shown in 3.
Wherein, the test voltage purpose is to have no abnormal in order to investigate the preliminary filling process, such as the setting in size of current and charging interval, the stability of charging process cabinet point electric current etc., contrast 0.1C charge graph is judged, the magnitude of voltage size should be identical under identical charge capacity, error is got rid of the disturbing factor that back finished product electricity core performance is investigated at ± 0.01V.
The preliminary filling process is the process that a SEI film and side reaction thereof take place, if the preliminary filling electric weight is not enough or preliminary filling does not produce a desired effect, if such as have gas not discharge fully, electric core after the cleaning just has the phenomenon of bulging shell, therefore measures cleaning back size and can reflect the preliminary filling effect to a certain extent.Under identical preliminary filling condition, its preliminary filling effect comparatively speaking that the cleaning size is little is relatively good.
Investigating electric in-core resistance is that the film formed performance of SEI is good because the bright interface performance of internal resistance novel is good.The influencing factor of electricity in-core resistance is many, such as positive and negative lug is welded with no rosin joint, different material, material mixture ratio, method for pre-charging etc.Carry out different method for pre-charging experiments because our selected electric core is the electric core of same batch of production, therefore can get rid of the interference that outer all the other operations of method for pre-charging are brought as far as possible.Select identical materials, identical electrode density, thickness in other words for use, determine that the normal volume of lug welding core carries out the method for pre-charging experiment.If method for pre-charging is unreasonable, cause pole piece to have the part to overcharge, analyse situations such as lithium, internal resistance this moment is just accordingly than higher, so resistance can be used as the index that charging effect is reacted in the side in the embodiments of the invention.
And electric core is charged to 3.92V, investigating its change in size situation then is the usual index that battery industry is investigated electric core end properties.
Equally, other embodiment and Comparative Examples 1,3 adopt identical step, and just the time and the electric current of method for pre-charging employing are different.
Comparative Examples 2,4 is a traditional handicraft, except that fluid injection to adopt disposable 100% fluid injection, method for pre-charging be shown in the table 1 and digestion time 12～16h different, other steps are identical with above embodiment.
The method for pre-charging of all embodiment and Comparative Examples is shown in Table 1, and its technique effect data see Table 3.
The method for pre-charging of each embodiment of table 1. and Comparative Examples
Table 2. partial volume system
Lithium cell changes into the capacity of obtaining here, and knows the size of capacity, is exactly partial volume.By partial volume, determined the grade of electric core.
Each embodiment of table 3. and Comparative Examples technique effect
Embodiment 1～16 shows with the data of Comparative Examples 2 and embodiment 17～21 and Comparative Examples 4, by selecting method for pre-charging of the present invention for use, electric core is reached and the suitable even more excellent electric property of electric core that adopts traditional preliminary filling technology, simultaneously can greatly reduce pre-charging time, enhance productivity.And embodiment 1～16 understands the necessity of first low current charge with Comparative Examples 1 and embodiment 17～21 with the tables of data of Comparative Examples 4, if it is all poorer not carry out the effects such as its finished product electricity core size of words, capacity performance and cycle performance of the little pre-charge of the first step.
The present invention can shorten the pre-charging time of electric core by introducing big pre-charge, and further optimizing positive active material is that the method for pre-charging lithium ion batteries that cobalt acid lithium and nickle cobalt lithium manganate mix is 0.05C, 10min 0.4C, 22min.The method for pre-charging of this optimization be by above each embodiment laterally, longitudinally the contrast, the data that best embody the method for pre-charging quality are anodal gram volume and cycle performance and pre-charging time, investigate combination properties such as its internal resistance and size again, thereby contrast draws optimized method for pre-charging.
In the preliminary filling process of lithium ion battery, increase along with nickel ternary cobalt manganic acid lithium ratio in the positive active material, preliminary filling SEI film forming process side reaction aerogenesis, the corresponding increase of its time meeting of exhaust process, therefore, the lithium ion battery that method for pre-charging lithium ion batteries of the present invention was suitable for, it has the certain limit requirement to the ratio that cobalt acid lithium and nickle cobalt lithium manganate in the positive active material mix, be that the shared weight percentage of cobalt acid lithium should be 60%～80%, nickle cobalt lithium manganate is shared to should be 20%～40%.
Selected in the above embodiment of the present invention is the electric core of 1000mAh, electric core for other amount of capacity, only need satisfy positive active material is the mixing of cobalt acid lithium and nickle cobalt lithium manganate, the mixed proportion scope accounts for 60%～80% at cobalt acid lithium, nickle cobalt lithium manganate accounts for 20%～40%, and method for pre-charging then of the present invention is suitable equally to it.But, consider if the nominal capacity of lithium ion battery cell is excessive, during greater than 1500mAh, because the charging current in corresponding second step of method for pre-charging is bigger, current error to this preliminary filling cabinet is bigger, or stability is poor, can cause certain influence to electric core performance thus.Consider the also not commercialization on a large scale with respect to the sour lithium of cobalt of nickel ternary cobalt manganic acid lithium positive electrode simultaneously, moreover the ratio of its mixing limits, if its side reaction aerogenesis exhaust of excessive its preliminary filling process of capacity is than theoretic complexity, time, also the president was a lot, therefore, the electric core range of capacity that method for pre-charging of the present invention was fit to is less than 1500mAh, preferably less than 1200mAh.
The lithium ion battery that method for pre-charging of the present invention was suitable for, nickle cobalt lithium manganate preferred elements ratio in its positive active material satisfies Ni: Co: Mn=1/3: 1/3: 1/3 nickle cobalt lithium manganate, and used nickle cobalt lithium manganate in the specific embodiment of the invention and all embodiment, Comparative Examples, its molecular formula is LiNi
1/3Co
1/3Mn
1/3O
2
The enforcement of method for pre-charging of the present invention will make the nickle cobalt lithium manganate ternary material use widely and accomplish fluently solid foundation.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (9)
1. method for pre-charging lithium ion batteries, the positive active material of described lithium ion battery is the composite material of cobalt acid lithium and nickle cobalt lithium manganate, it is characterized in that: the method for pre-charging of described lithium ion battery is to adopt stage charging, described stage charging comprises at least two charge step, the charging current of second charge step is greater than the charging current of first charge step, and total preliminary filling electric weight of first charge step and second charge step is 15%～35% of the total electric weight of described lithium ion battery.
2. a kind of method for pre-charging lithium ion batteries according to claim 1 is characterized in that: total preliminary filling electric weight of first charge step and second charge step is 15%～30% of the total electric weight of described lithium ion battery.
3. a kind of method for pre-charging lithium ion batteries according to claim 1 and 2 is characterized in that: in the positive active material of described lithium ion battery, cobalt acid lithium accounts for 60%～80%, and nickle cobalt lithium manganate accounts for 20%～40%, described being weight percentage.
4. a kind of method for pre-charging lithium ion batteries according to claim 3 is characterized in that: the charging current of described first charge step is that the charging interval is 5～30min less than 0.1C.
5. a kind of method for pre-charging lithium ion batteries according to claim 4 is characterized in that: the charging current of described first charge step is 0.05C～0.1C, and the charging interval is 5～15min.
6. a kind of method for pre-charging lithium ion batteries according to claim 3 is characterized in that: the charging current of described second charge step is 0.3C～0.6C, and the charging interval is 10～60min.
7. a kind of method for pre-charging lithium ion batteries according to claim 4 is characterized in that: the charging current of described second charge step is 0.3C～0.6C, and the charging interval is 10～60min.
8. a kind of method for pre-charging lithium ion batteries according to claim 7 is characterized in that: the charging current of described first charge step is 0.05C, and the charging interval is 10min, and the charging current of second charge step is 0.4C, and the charging interval is 22min.
9. a kind of method for pre-charging lithium ion batteries according to claim 1 is characterized in that: the injecting electrolytic solution amount before the described stage charging is 80%～85%, and electrolyte 15%～10% reinjects after the stage charging.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910105010A CN101783424A (en) | 2009-01-15 | 2009-01-15 | Method for pre-charging lithium ion battery |
| PCT/CN2010/070202 WO2010081422A1 (en) | 2009-01-15 | 2010-01-15 | Pre-charging method for lithium-ion battery |
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| CN200910105010A CN101783424A (en) | 2009-01-15 | 2009-01-15 | Method for pre-charging lithium ion battery |
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| CN101783424A true CN101783424A (en) | 2010-07-21 |
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| CN103066329A (en) * | 2011-10-24 | 2013-04-24 | 深圳市比克电池有限公司 | Lithium ion battery activation method |
| CN103117412A (en) * | 2013-01-31 | 2013-05-22 | 深圳市海太阳实业有限公司 | Lithium ion battery and formation method thereof |
| CN103187596A (en) * | 2011-12-28 | 2013-07-03 | 上海空间电源研究所 | Stabilization method for lithium-enriched composite anode material with high specific capacity |
| CN103187590A (en) * | 2011-12-27 | 2013-07-03 | 比亚迪股份有限公司 | Formation method for lithium ion battery and lithium ion battery |
| CN105322245A (en) * | 2014-07-31 | 2016-02-10 | 中信国安盟固利动力科技有限公司 | Charging method for improving charging efficiency of lithium ion battery |
| CN105762417A (en) * | 2016-04-05 | 2016-07-13 | 东莞市创明电池技术有限公司 | Method for prolonging service life of cylindrical lithium-ion battery |
| CN108183273A (en) * | 2017-12-26 | 2018-06-19 | 北京康力优蓝机器人科技有限公司 | A kind of charging method of the safety of lithium ion secondary battery of smart home |
| CN109581234A (en) * | 2018-11-07 | 2019-04-05 | 上海恩捷新材料科技有限公司 | A kind of lithium ion battery conformity classification method |
| CN109888401A (en) * | 2019-04-16 | 2019-06-14 | 上海卡耐新能源有限公司 | A kind of chemical synthesizing method solving soft lithium ion packet power battery exception |
| CN110994037A (en) * | 2019-12-30 | 2020-04-10 | 山东聚信新能源科技有限公司 | Full-voltage formation method and equipment for flexible package lithium ion battery |
| CN112946503A (en) * | 2019-12-11 | 2021-06-11 | 珠海冠宇电池股份有限公司 | Method for rapidly testing cycle life of lithium ion battery |
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Cited By (17)
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| CN103066329B (en) * | 2011-10-24 | 2015-06-17 | 深圳市比克电池有限公司 | Lithium ion battery activation method |
| CN103066329A (en) * | 2011-10-24 | 2013-04-24 | 深圳市比克电池有限公司 | Lithium ion battery activation method |
| CN103187590A (en) * | 2011-12-27 | 2013-07-03 | 比亚迪股份有限公司 | Formation method for lithium ion battery and lithium ion battery |
| CN103187590B (en) * | 2011-12-27 | 2015-05-13 | 比亚迪股份有限公司 | Formation method for lithium ion battery and lithium ion battery |
| CN103187596A (en) * | 2011-12-28 | 2013-07-03 | 上海空间电源研究所 | Stabilization method for lithium-enriched composite anode material with high specific capacity |
| CN103117412B (en) * | 2013-01-31 | 2016-08-03 | 深圳市海太阳实业有限公司 | Lithium ion battery and chemical synthesizing method thereof |
| CN103117412A (en) * | 2013-01-31 | 2013-05-22 | 深圳市海太阳实业有限公司 | Lithium ion battery and formation method thereof |
| CN105322245A (en) * | 2014-07-31 | 2016-02-10 | 中信国安盟固利动力科技有限公司 | Charging method for improving charging efficiency of lithium ion battery |
| CN105322245B (en) * | 2014-07-31 | 2018-01-09 | 中信国安盟固利动力科技有限公司 | A kind of charging method for improving lithium ion battery charge efficiency |
| CN105762417A (en) * | 2016-04-05 | 2016-07-13 | 东莞市创明电池技术有限公司 | Method for prolonging service life of cylindrical lithium-ion battery |
| CN108183273A (en) * | 2017-12-26 | 2018-06-19 | 北京康力优蓝机器人科技有限公司 | A kind of charging method of the safety of lithium ion secondary battery of smart home |
| CN109581234A (en) * | 2018-11-07 | 2019-04-05 | 上海恩捷新材料科技有限公司 | A kind of lithium ion battery conformity classification method |
| CN109581234B (en) * | 2018-11-07 | 2021-01-26 | 上海恩捷新材料科技有限公司 | Lithium ion battery consistency screening method |
| CN109888401A (en) * | 2019-04-16 | 2019-06-14 | 上海卡耐新能源有限公司 | A kind of chemical synthesizing method solving soft lithium ion packet power battery exception |
| CN109888401B (en) * | 2019-04-16 | 2022-06-28 | 上海卡耐新能源有限公司 | Formation method for solving abnormity of soft package lithium ion power battery |
| CN112946503A (en) * | 2019-12-11 | 2021-06-11 | 珠海冠宇电池股份有限公司 | Method for rapidly testing cycle life of lithium ion battery |
| CN110994037A (en) * | 2019-12-30 | 2020-04-10 | 山东聚信新能源科技有限公司 | Full-voltage formation method and equipment for flexible package lithium ion battery |
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