Had a look at the journal now. Nothing obvious. iwd just fails telling me the key was invalid (which of course it is not as it works after the next boot). Unfortunately, only connmand is verbose, iwd not so much:
QuoteDisplay MoreLibreELEC iwd[469]: event: connect-failed, status: 16
LibreELEC iwd[469]: event: state, old: connecting, new: disconnected
LibreELEC iwd[469]: event: state, old: disconnected, new: autoconnect_quick
LibreELEC connmand[651]: ../plugins/iwd.c:cm_network_connect_cb() /net/connman/iwd/0/3/465249545a21426f78203735323020574f_psk connect failed: net.connman.iwd.Failed
LibreELEC connmand[651]: ../src/network.c:connman_network_set_error() network 0xef27a60 error 3
LibreELEC connmand[651]: ../src/service.c:__connman_service_indicate_error() service 0xef27cb0 error 7
LibreELEC connmand[651]: ../src/service.c:set_error() service 0xef27cb0 (wifi_d83add53bde1_465249545a21426f78203735323020574f_managed_psk) error 7 (invalid-key)
LibreELEC connmand[651]: Interface wlan0 [ wifi ] error "invalid-key"
LibreELEC connmand[651]: ../src/service.c:__connman_service_ipconfig_indicate_state() service 0xef27cb0 (wifi_d83add53bde1_465249545a21426f78203735323020574f_managed_psk) type 1 (IPv4) old state 3 (configuration) new state 7 (failure)
LibreELEC connmand[651]: ../src/ipconfig.c:__connman_ipconfig_disable() ipconfig 0xef27ff0
LibreELEC connmand[651]: ../src/ipconfig.c:__connman_ipconfig_unref_debug() 0xef27ff0 ref 2 by ../src/ipconfig.c:1998:__connman_ipconfig_disable()
LibreELEC connmand[651]: ../src/service.c:service_indicate_state() service 0xef27cb0 (wifi_d83add53bde1_465249545a21426f78203735323020574f_managed_psk) old configuration - new failure/idle => failure
LibreELEC connmand[651]: Interface wlan0 [ wifi ] state is failure
LibreELEC connmand[651]: ../plugins/vpn.c:vpn_disconnect_check()
LibreELEC connmand[651]: ../src/session.c:service_state_changed() service 0xef27cb0 (wifi_d83add53bde1_465249545a21426f78203735323020574f_managed_psk) state 7
LibreELEC connmand[651]: ../src/provider.c:provider_service_changed() service 0xef27cb0 wifi_d83add53bde1_465249545a21426f78203735323020574f_managed_psk state 7 index 3/-1
LibreELEC connmand[651]: ../src/notifier.c:notify_idle_state() idle 1
LibreELEC connmand[651]: ../src/manager.c:idle_state() idle 1
LibreELEC connmand[651]: ../src/agent.c:connman_agent_report_error_full() agent (nil) sender (null) context 0xef27cb0 path -
LibreELEC connmand[651]: ../src/service.c:service_save() service 0xef27cb0 (wifi_d83add53bde1_465249545a21426f78203735323020574f_managed_psk) new 0
LibreELEC connmand[651]: ../src/ipconfig.c:__connman_ipconfig_save() ipconfig 0xef27ff0 identifier wifi_d83add53bde1_465249545a21426f78203735323020574f_managed_psk method dhcp
LibreELEC connmand[651]: ../src/ipconfig.c:__connman_ipconfig_save() ipconfig 0xef280d0 identifier wifi_d83add53bde1_465249545a21426f78203735323020574f_managed_psk method off
LibreELEC connmand[651]: ../src/service.c:service_list_sort() from service_indicate_state()
LibreELEC connmand[651]: ../src/gateway.c:__connman_gateway_update()
LibreELEC connmand[651]: ../src/gateway.c:gateway_data_debug() from __connman_gateway_update() default_gateway (nil)
LibreELEC connmand[651]: ../src/gateway.c:__connman_gateway_update() updated4 0 updated6 0
LibreELEC connmand[651]: ipconfig state 7 ipconfig method 1
LibreELEC connmand[651]: ../src/network.c:__connman_network_disconnect() network 0xef27a60
LibreELEC connmand[651]: ../src/network.c:connman_network_set_associating() network 0xef27a60 associating 0
LibreELEC connmand[651]: ../src/network.c:set_disconnected() service 0xef27cb0 ipv4 0xef27ff0 ipv6 0xef280d0
LibreELEC connmand[651]: ../src/network.c:set_disconnected() method ipv4 4 ipv6 1
LibreELEC connmand[651]: ../src/dhcp.c:__connman_dhcp_stop() ipconfig_table 0xef10400 ipconfig 0xef27ff0
LibreELEC iwd[469]: event: state, old: autoconnect_full, new: disconnected