JPWO2019191837A5 - - Google Patents
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- JPWO2019191837A5 JPWO2019191837A5 JP2020545801A JP2020545801A JPWO2019191837A5 JP WO2019191837 A5 JPWO2019191837 A5 JP WO2019191837A5 JP 2020545801 A JP2020545801 A JP 2020545801A JP 2020545801 A JP2020545801 A JP 2020545801A JP WO2019191837 A5 JPWO2019191837 A5 JP WO2019191837A5
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- lithium
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- metal
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- 239000002243 precursor Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 32
- 239000010406 cathode material Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000006182 cathode active material Substances 0.000 claims description 9
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims description 3
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229910021450 lithium metal oxide Inorganic materials 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 238000005549 size reduction Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical group 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims 2
- 230000007420 reactivation Effects 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 7
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
したがって、本発明によると、上述の目標、目的及び利点を完全に満たす、プロセス、製品及び電池が提供されることは明らかである。本発明の特定の態様を説明してきたが、その代替例、改変例及び変形例が当業者に示唆され得ること、並びに本明細書は、特許請求の範囲内に入るような代替例、改変例及び変形例を全て包含することを意図していることが理解される。
以下に、本願の出願当初の請求項を実施の態様として付記する。
［１］ リチウムイオン電池の生産に使用するためのカソード活物質としてのリチウム混合金属酸化物を生産するプロセスであって、当該プロセスは、以下の２つの主要な工程、すなわち、前駆体調製工程及びリチウム化工程を含むプロセス、
Ａ）前記前駆体調製工程では、固体状の金属を、好ましくは酸素、金属硝酸塩及び硝酸、又はこれらの組合せから選択される、少なくとも１つの酸化剤、及び必要に応じてシード混合金属水酸化物粒子を含有する水溶液が含まれる反応器である撹拌反応システムに添加して、前記金属の酸化をアルカリ条件下で行い、
全体の酸化反応は、以下の式：
ｘＭｅ ＋ ｙＭｅ’（ＮＯ
３
）
ｎ
＋ ｚＨＮＯ
３
＋ （０．２５ｘｍ－２ｙｎ－２ｚ）Ｏ
２
＋ （０．５ｘｍ＋２ｙｎ＋ｚ）Ｈ
２
Ｏ → Ｍｅ
ｘ
Ｍｅ’
ｙ
（ＯＨ）
（ｘｍ＋ｙｎ）
＋ （ｙｎ＋ｚ）ＮＨ
３
（ここで、
Ｍｅはニッケル、マンガン、コバルト、アルミニウム及びマグネシウムからなる群より選択される少なくとも１つの金属を表し、
Ｍｅ’はニッケル、マンガン、コバルト、アルミニウム、マグネシウム、ジルコニウム、イットリウム、チタン、バナジウム及びモリブデンからなる群より選択される少なくとも１つの金属のイオンを表し、
Ｍｅ
ｘ
Ｍｅ’
ｙ
（ＯＨ）
（ｘｍ＋ｙｎ）
は前駆体を表し、
ｘ及びｙはそれぞれＭｅ及びＭｅ’のモル分率であり、ｍは前記前駆体におけるＭｅのモル加重平均化学原子価であり、ｎは反応物におけるＭｅ’のモル加重平均化学原子価であり、ｚは前記反応システムに導入されたＨＮＯ
３
のモル分率であり、
ｘｍ≧８ｙｎ＋８ｚであり、ｘ＋ｙ＝１であり、１≧ｘ＞０であり、ｙ≧０、ｚ≧０である）
によって表され、
前記酸化反応からの合成スラリーを前記反応器から取り出し、未反応金属を前記スラリーから除去して前記反応システムに再循環させ、その後、固液分離を行い、回収された固体は回収された前駆体として使用し、液体を好ましくはいかなる処理も行わずに直接前記反応システムに再循環させ、並びに
Ｂ）前記リチウム化工程では、前記回収された前駆体をリチウム含有化合物及び必要に応じて他のドーパントと混合して最終混合物を生成し、続いて前記最終混合物を焼成してカソード活物質を得る。
［２］ 前記前駆体調製工程における反応条件は、反応中スラリーのｐＨを７．５～１３とし、温度を２０℃～前記スラリーの沸点とすることを含む、［１］に記載のカソード材を生産する方法。
［３］ 前記溶液に、硫酸、硝酸若しくは酢酸から選択されるいずれかの酸を添加することによって、及び／又は、水酸化リチウム若しくは酸化リチウム、水酸化ナトリウム若しくは酸化ナトリウム、水酸化カリウム若しくは酸化カリウム、若しくはアンモニアから選択されるアルカリ性物質を添加することによって前記溶液の前記ｐＨを調整する、［２］に記載のカソード材を生産する方法。
［４］ 前記水溶液は導電性を増大させるために溶解塩も含有する、［１］に記載のカソード材を生産する方法。
［５］ 前記溶解塩は、ナトリウム、リチウム、カリウム及びアンモニウムから選択される陽イオンとの、硫酸塩、酢酸塩、硝酸塩及び塩素酸塩から選択される、［４］に記載のカソード材を生産する方法。
［６］ 前記水溶液は、前記水溶液中の前記金属イオンとキレートを形成する錯化剤も含有する、［１］に記載のカソード材を生産する方法。
［７］ 前記錯化剤はアンモニア及びアンモニウムの混合物を含む、［６］に記載のカソード材を生産する方法。
［８］ 前記酸化剤は、空気、酸素、金属硝酸塩若しくは硝酸、又は同時に使用される２つ以上の酸化剤の組合せである、［１］に記載のカソード材を生産する方法。
［９］ 前記酸化剤は酸素である、［１］に記載のカソード材を生産する方法。
［１０］ 前記酸素は他のガスに含有されている、［９］に記載のカソード材を生産する方法。
［１１］ 前記前駆体調製工程における前記反応システムは少なくとも１つの攪拌タンクを含む、［１］に記載のカソード材を生産する方法。
［１２］ 前記固液分離工程からの液体を用いたミリング及び／又は洗浄によって前記未反応金属を再活性化する、［１］に記載のカソード材を生産する方法。
［１３］ 前記前駆体調製工程における反応を連続操作モードで定常状態条件下で操作する、［１］～［１２］のいずれか１つに記載のカソード材を生産する方法。
［１４］ 前記金属を常時同じ比率で連続的に添加して各粒子中に均一な元素分布を有する前駆体を生産するか、又は前記金属を経時的に異なる比率で連続的に添加して各粒子中に不均一な元素分布を有する前駆体を生産する、［１３］に記載のカソード材を生産する方法。
［１５］ 前記固液分離後に回収された液体の少なくとも９０％を前記反応システムに直接再循環させる、［１］に記載のカソード材を生産する方法。
［１６］ 前記前駆体と同じか又は同様の組成を有するが前記前駆体よりも粒径の小さい固体粒子を、反応の始め及び／又は反応中に前記反応システムに導入する、［１］に記載のカソード材を生産する方法。
［１７］ 前記液体と同じ又は同様の組成を有する人工溶液を調製し、適切なろ液がろ過システムから生成されるまで反応の始動のために使用し、次いで前記反応システムに再循環させる、［１］に記載のカソード材を生産する方法。
［１８］ 前記固体を乾燥させて前記前駆体を得ること、前記前駆体をリチウム含有化合物と混合すること、この混合物を焼成すること、及びこれによりカソード活物質を得ることをさらに含む、［１］に記載のカソード材を生産する方法。
［１９］ 前記得られたカソード活物質をサイズ減少操作に供する、［１８］に記載のカソード材を生産する方法。
［２０］ 前記リチウム含有化合物は結晶水を伴う又は伴わない水酸化リチウム、及び炭酸リチウムである、［１］に記載のカソード材を生産する方法。
［２１］ 前記最終混合物を６００℃～１１００℃で焼成する、［１］に記載のカソード材を生産する方法。
［２２］ カソード材を焼成後さらなる処理に供し、前記さらなる処理は、余分なリチウム及び不純物を除去するための洗浄、並びに電池生産中及び／又は電池使用中に前記カソード材の性能を向上させるための前記カソード材の被覆を含む、［１］に記載のカソード材を生産する方法。
［２３］ ［１］～［２２］のいずれか１つに記載のプロセスに従って製造された、リチウムイオン二次電池用カソード活物質として使用するためのリチウム混合金属酸化物。
［２４］ カソード材としてリチウム金属酸化物を含むリチウム二次電池であって、前記カソード材は［１］～［２２］のいずれか１つに記載のプロセスに従って製造された混合金属酸化物であるリチウム二次電池。
Therefore, according to the present invention, it is clear that a process, product and battery that completely meets the above-mentioned goals, objectives and advantages will be provided. Although specific embodiments of the present invention have been described, alternatives, modifications and variations thereof can be suggested to those skilled in the art, and the present specification is examples of alternatives and modifications that fall within the scope of the claims. And it is understood that it is intended to include all modifications.
Hereinafter, the claims at the time of filing the application of the present application are added as embodiments.
[1] A process for producing a lithium mixed metal oxide as a cathode active material for use in the production of a lithium ion battery, which is the following two main steps, that is, a precursor preparation step and a precursor preparation step. Processes involving the lithiumization process,
A) In the precursor preparation step, the solid metal is preferably selected from oxygen, metal nitrate and nitrate, or a combination thereof, at least one oxidant, and optionally a seed mixed metal hydroxide. It is added to a stirring reaction system, which is a reactor containing an aqueous solution containing particles, to oxidize the metal under alkaline conditions.
The overall oxidation reaction is as follows:
xMe + yMe'(NO 3 ) n + zHNO 3 + (0.25xm-2yn-2z) O 2 + (0.5xm + 2yn + z) H 2 O → Me x Me'y ( OH) (xm + yn) + (yn + z) NH 3
(here,
Me represents at least one metal selected from the group consisting of nickel, manganese, cobalt, aluminum and magnesium.
Me'represents the ion of at least one metal selected from the group consisting of nickel, manganese, cobalt, aluminum, magnesium, zirconium, yttrium, titanium, vanadium and molybdenum.
Me x Me'y (OH) (xm + yn) represents a precursor and represents a precursor.
x and y are the mole fractions of Me and Me', respectively, m is the mole-weighted average chemical valence of Me in the precursor, and n is the mole-weighted average chemical valence of Me'in the reactants. z is the mole fraction of HNO 3 introduced into the reaction system .
xm ≧ 8 yn + 8z, x + y = 1, 1 ≧ x> 0, y ≧ 0, z ≧ 0)
Represented by
The synthetic slurry from the oxidation reaction is removed from the reactor, the unreacted metal is removed from the slurry and recirculated to the reaction system, followed by solid-liquid separation and the recovered solid is the recovered precursor. The liquid is preferably recirculated directly into the reaction system without any treatment, as well as
B) In the lithium conversion step, the recovered precursor is mixed with a lithium-containing compound and, if necessary, another dopant to form a final mixture, and then the final mixture is calcined to obtain a cathode active material. ..
[2] The cathode material according to [1], wherein the reaction conditions in the precursor preparation step include setting the pH of the slurry during the reaction to 7.5 to 13 and the temperature from 20 ° C to the boiling point of the slurry. How to produce.
[3] By adding any acid selected from sulfuric acid, nitric acid or acetic acid to the solution, and / or lithium hydroxide or lithium oxide, sodium hydroxide or sodium oxide, potassium hydroxide or potassium oxide. Or, the method for producing a cathode material according to [2], wherein the pH of the solution is adjusted by adding an alkaline substance selected from ammonia.
[4] The method for producing a cathode material according to [1], wherein the aqueous solution also contains a dissolved salt in order to increase conductivity.
[5] The dissolved salt produces the cathode material according to [4], which is selected from sulfates, acetates, nitrates and chlorates with cations selected from sodium, lithium, potassium and ammonium. how to.
[6] The method for producing a cathode material according to [1], wherein the aqueous solution also contains a complexing agent that forms a chelate with the metal ions in the aqueous solution.
[7] The method for producing a cathode material according to [6], wherein the complexing agent contains a mixture of ammonia and ammonium.
[8] The method for producing a cathode material according to [1], wherein the oxidizing agent is air, oxygen, metal nitrate or nitric acid, or a combination of two or more oxidizing agents used at the same time.
[9] The method for producing a cathode material according to [1], wherein the oxidizing agent is oxygen.
[10] The method for producing a cathode material according to [9], wherein the oxygen is contained in another gas.
[11] The method for producing a cathode material according to [1], wherein the reaction system in the precursor preparation step includes at least one stirring tank.
[12] The method for producing a cathode material according to [1], wherein the unreacted metal is reactivated by milling and / or washing with a liquid from the solid-liquid separation step.
[13] The method for producing a cathode material according to any one of [1] to [12], wherein the reaction in the precursor preparation step is operated in a continuous operation mode under steady state conditions.
[14] The metal is always continuously added at the same ratio to produce a precursor having a uniform element distribution in each particle, or the metal is continuously added at different ratios over time. The method for producing a cathode material according to [13], which produces a precursor having a non-uniform element distribution in the particles.
[15] The method for producing a cathode material according to [1], wherein at least 90% of the liquid recovered after the solid-liquid separation is directly recirculated to the reaction system.
[16] The solid particles having the same or similar composition as the precursor but having a smaller particle size than the precursor are introduced into the reaction system at the beginning and / or during the reaction, according to [1]. How to produce cathode materials.
[17] An artificial solution having the same or similar composition as the liquid is prepared, used to initiate the reaction until a suitable filtrate is produced from the filtration system, and then recirculated to the reaction system [1]. ] The method for producing the cathode material according to the above.
[18] Further comprising drying the solid to obtain the precursor, mixing the precursor with a lithium-containing compound, firing the mixture, and thereby obtaining a cathode active material [1]. ] A method for producing the cathode material according to the above.
[19] The method for producing a cathode material according to [18], wherein the obtained cathode active material is subjected to a size reduction operation.
[20] The method for producing a cathode material according to [1], wherein the lithium-containing compound is lithium hydroxide with or without water of crystallization and lithium carbonate.
[21] The method for producing a cathode material according to [1], wherein the final mixture is calcined at 600 ° C to 1100 ° C.
[22] The cathode material is subjected to further treatment after firing, and the further treatment is for cleaning to remove excess lithium and impurities, and for improving the performance of the cathode material during battery production and / or battery use. The method for producing a cathode material according to [1], which comprises the coating of the cathode material according to the above.
[23] A lithium mixed metal oxide for use as a cathode active material for a lithium ion secondary battery, which is produced according to the process according to any one of [1] to [22].
[24] A lithium secondary battery containing a lithium metal oxide as a cathode material, wherein the cathode material is a mixed metal oxide produced according to the process according to any one of [1] to [22]. Lithium secondary battery.
Claims (26)
前駆体調製工程では、アルカリ条件下で、選択された金属の粒子を、前記金属の粒子、水溶液及び少なくとも１つの酸化剤を含む混合物を含有する反応システムに添加して、前駆体及び未反応金属を含むスラリーを形成させ、ここで、前記選択された金属は、ニッケル、マンガン、コバルト、アルミニウム及びマグネシウムからなる群より選択され、
再循環工程では、前記未反応金属を前記スラリーから分離して第一の溶液を形成させ、前記前駆体を前記第一の溶液から分離して第二の溶液を形成させ、前記未反応金属及び第二の溶液を直接前記反応システムに再循環させ、並びに
リチウム化工程では、前記回収された前駆体をリチウム含有化合物と混合して最終混合物を生成させ、前記最終混合物を焼成してリチウム混合金属酸化物のカソード活物質を得る、
ことを含む方法。 A method for producing a cathode active material of a lithium mixed metal oxide for use in a lithium ion battery .
In the precursor preparation step, under alkaline conditions, selected metal particles are added to a reaction system containing the metal particles , an aqueous solution and a mixture containing at least one oxidizing agent to add the precursor and the precursor. A slurry containing an unreacted metal is formed , wherein the selected metal is selected from the group consisting of nickel, manganese, cobalt, aluminum and magnesium .
In the recirculation step, the unreacted metal is separated from the slurry to form a first solution, the precursor is separated from the first solution to form a second solution, and the unreacted metal and The second solution is recirculated directly into the reaction system, as well as
In the lithium conversion step, the recovered precursor is mixed with a lithium-containing compound to form a final mixture, and the final mixture is calcined to obtain a cathode active material of a lithium mixed metal oxide .
How to include that .
A lithium secondary battery containing a lithium metal oxide as a cathode material, wherein the cathode material is a mixed metal oxide produced by the method according to any one of claims 1 to 24 .
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| KR102430686B1 (en) * | 2021-12-28 | 2022-08-10 | (주)에코프로머티리얼즈 | Hydrometallurgical recovery method of nickel sulfate |
| CN115465899B (en) * | 2022-09-14 | 2023-09-15 | 陕西红马科技有限公司 | Multi-crown multi-element spherical coating type precursor, preparation method thereof, chemical coating modified product and chemical coating modified method |
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| EP0388808B1 (en) * | 1989-03-20 | 1994-06-15 | Inco Limited | Nickel hydroxide |
| US5264201A (en) * | 1990-07-23 | 1993-11-23 | Her Majesty The Queen In Right Of The Province Of British Columbia | Lithiated nickel dioxide and secondary cells prepared therefrom |
| ES2108820T3 (en) * | 1992-06-15 | 1998-01-01 | Inco Ltd | PROCEDURE FOR PRODUCING NICKEL HYDROXIDE. |
| US5824283A (en) * | 1997-04-28 | 1998-10-20 | Inco Limited | Process for producing nickel hydroxide from elemental nickel |
| TW434187B (en) * | 1997-05-07 | 2001-05-16 | Fuji Chem Ind Co Ltd | A process for preparing a spinel type of lithium manganese complex oxide |
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| CN104409723B (en) | 2014-12-25 | 2016-09-28 | 芜湖华欣诺电化学科技有限公司 | A kind of electrochemical preparation method of tertiary cathode material |
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